Nhl palladium heterogeneous complexes and their uses as recoverable catalysts (Machine-translation b

专利摘要:
The present invention comprises a process for the preparation of new palladium N-heterocyclic carbene complexes (cps) which, once formed, can be heterogeneized on magnetic particles (pms), providing magnetic particles with the supported complexes (pmcs) with palladium species. Unique, well defined and firmly fixed to the support. The pmcs are characterized by giving rise to stable dispersions in aqueous media, they are active in catalytic processes of carbon-carbon coupling in these media and in mild conditions, the superparamagnetism of the core of the particles allows their separation from the products by applying a magnetic field, they recover without degradation, they can be reused reaching very high values of ton and do not suffer metallic leachate, or it is insignificant, resulting in products of catalysis with palladium contents below 10 ppm by mass (up to levels of about ppb) after the magnetic separation of the particles. (Machine-translation by Google Translate, not legally binding)
公开号:ES2555613A1
申请号:ES201400505
申请日:2014-06-26
公开日:2016-01-05
发明作者:Francisco José MARTÍNEZ OLID；Román ANDRÉS HERRANZ；Ernesto DE JESÚS ALCANIZ；Juan Carlos Flores Serrano；Karine HEUZÉ；Luc VELLUTINI
申请人:Universidad de Alcala de Henares UAH；
IPC主号:

专利说明:

 and iii) heterogeneization or immobilization of soluble metal complex to insoluble supports, both organic and inorganic.  In general, these attempts have not resulted in commercially viable processes for various reasons, finding that the most frequent are the leachate of the active center and / or its degradation, which result in the metal contamination of the products and / or fatal losses of productivity, activity and selectivity.  The particular case of palladium, known for its usefulness in catalyzing a wide range of transformations in organic synthesis, conventionally associated with organophosphorus ligands, is no exception: very few industrial processes are implemented in which their soluble complexes (de Vries) are involved. J.  G.  2012) and in them it has generally been necessary to develop specific and expensive procedures to eliminate metallic and phosphorus toxic residues.  Segan de Vries, in the five years prior to 2012, only 6-7% of the synthetic stages of the pharmaceutical industry 15 involved homogenous catalysis, highlighting that 50% of them corresponded to the most recently introduced drugs.  It would therefore be desirable to have catalysts, in particular palladium and phosphorus-free ligands, that combine a distinctive behavior with high values of 20 TON (of the English turnover number), with which to arrive to implement "clean productions" in which they can be separated easily and efficiently, making it possible to reuse them, or use them continuously, and in which the expensive operations of metal purification of the products can be dispensed with.  25 Some ligands that have recently appeared as a very attractive alternative to organophosphates are those of the N-heterocyclic carbine (NHC) type.  NHCs provide strong bonds, which result in very robust and excellent metal complexes to catalyze a very wide range of processes in the homogeneous phase, in which the stereo-electronic characteristics of the ligand play an important stabilizing role 30 (Diez-Gonzalez, S. , etal.  2009).  To immobilize metal catalysts, among other supports currently available, magnetic nanoparticles (NPMs) have been used with various types of ligands covalently anchored to the surface, (Baig, R.  B.  N. , et al.  2013; Shylesh, S. , et al.  35 2010).  There are also descriptions in which heterogeneized NHC palladium complexes have been used through alkylsilOxide groups on bare NPMs 3(Stevens, P.  D. , et al.  Chem  Commun.  2005; Zheng, Y. , et al.  2006), through benzyl groups on polystyrene coated NPMs (Stevens, P.  D. , et al.  Org.  Lett.  2005), and arylsiloxane groups on magnetic microspheres (Yang, H. , et al.  2012) or silicon coated NPMs (Yang, H. , et al.  2011).  All of them have been shown to be active in various cross-coupling reactions (i. and. , Suzuki-Miyaura, Heck-Mizoroki and Sonogashira), are magnetically recoverable and most have been reused.  Of the above only in one case (Yang, H. , etal.  2011) the content of palladium in the products has been determined, but only after the first use of the catalyst.  In all of them, the metal complex support procedure follows the sequence: 1) support functionalization with imidazolium salts, which are precursors of NHC ligands; 2) metalation of the previous functionalized support with acetylacetonate or palladium acetate aPd (acac) 2] 6 [Pd (OAc) 2]).  The disadvantage of this methodology, which on the other hand is the usual one with any type of support and ligand, is the impossibility of being able to control both the formation of corrplejos with a unique coordination environment, 15 as well as the presence of adsorbed and non-anchored metal remains covalently  In this sense, recently it has been found that, using silica gel as a support, the catalytic results are much better when the NHC complex of preformed palladium is immobilized than when it is synthesized on the surface of the silica gel (Tyrrell, E. , etal.  2011).  The present invention proposes the preparation of new palladium NHC complexes (CPs) and their subsequent heterogeneization on iron oxide magnetic particles (PMs), together with their use in cross-coupling reactions.  The method provides metallic species (bier, defined micas, in which NHC ligands strongly fix the metallic centers and protect them during catalysis, while being covalently supported through inert "Y" groups to particles coated with a material also inert, while the superparamagnetism of the nude ° of the particle to which they are associated allows its separation from the medium by applying a magnetic field °.  These magnetic particles with the supported catalysts (PMCs) give rise to stable dispersions in water, catalyze carbon-carbon coupling reactions in aqueous medium under mild conditions, even with aryl chlorides, recover without degradation by simple magnetic separation, can be reuse Arriving at very high TON values and do not suffer metallic leaching.  Concerning NHC ligand precursors substituted by terminal complementary groups (Gc) and the like or necessary to synthesize CPs of types I-111, 4 has been described.an imidazolium salt substituted with a protected amine in the form of a phthalimido group (Harjani, J.  R. , et al.  2008), three others substituted with a primary amine as a complementary group "G" (Busetto, L.  et al.  2008; Ballarin, B. , et al.  2012; Ohara, H. , et al.  2012), another five in which this group is triethoxysilyl (Chi, Y.  S. , et al.  2004; Trilla, M. , et 5 al.  2009; Borja, G. , et al.  2012, Berardi, S. , et al.  2010) and five others in which it is trimethoxysilyl (Kunze, K. , et al.  PCT / US2011 / 046155, Tyrrell, E. , et al.  2011).  As precursors necessary for the synthesis of type III complexes, the synthesis of bis (azolyl) alkanes (Ten-Bar, E, etal) have been described.  Heterocycles 1992, 34, 1365-1373).  A single example of mono CP (NHC) related to the formulation of type I is known, specifically with the NHC ligand substituted by a chain with a "G '= triethoxysilyl (Borja, G. , etal.  2012), although other related complexes have been described but without this type of substitution (Organ, M.  G. , et al.  CA2556850A1).  15 Bis CPs (NHC) have been described with the structure referred to as type II in which the "G" is trialkoxysilyl, using similar procedures (Kunze, K. , et a /.  PCT / US2011 / 046155; Tyrrell, E. , etal.  2011; Berardi, S. , etal.  2010), or different (Yang, H. , et al.  2009; Polshettiwar, V. , et al.  2008; Corma, A. , et al.  2007; Lee, S. -M. , et al.  2007, 79; Karimi, B. , et al.  2006), to employees in the context of the present invention.  In 20 series as similar procedures, the synthesis is performed through intermediate silver complexes, which are prepared following the standard method described by Lin (Wang, H.  M.  J. , et al.  1998), but in no case are these carbine transfer agents isolated, purified and characterized, unlike the procedure proposed in the present invention.  No type III CP with 25 alkoxysilyls has been described as "G", nor are there known of the types referred to herein as II and III in which that group is a primary amine, although both palladium complex topologies, chelate or not, they are abundant in the bibliography.  Procedures for supporting preformed CPs of types I and II already referred to have been described (i. and. , Gc = Si (OR) 3) on silicas of different nature, or to incorporate them in composite materials by means of sol-gel condensations, but in no case to generate PMCs.  As mentioned, if functionalized PMCs have been prepared with NHCs precursors immobilized to Saves alkoxysilyl groups on different supports that have subsequently been metalated with a source of palladium, but none on magnetic particles coated with silica of any kind, existing an example of fixing to this type of materials through arylsiloxane bonds as precedent plus 5nearby (Yang, H. , 2011).  In all of them the immobilization procedure used prevents knowing the identity and structural uniformity of the supported complexes.  Finally, a procedure for supporting palladium phosphan-type dendritic complexes 5, with a primary amine at the dendrOn focal point, on polymer-coated PMs with "carboxylic acid groups" such as "Gs" (Rosario-Amorin, D) . , et al.  2012).  The PMCs based on NHC ligands mentioned, although with a 10-entomb structure of the indeterminate palladium, have proven to be active in various cross-coupling processes under various reaction conditions, are magnetically recoverable and most have been reused.  Only in one case (Yang, H. , 2011) the leaching of palladium to the products has been determined and only after the first use of the catalyst.  DESCRIPTION OF THE INVENTION The present invention comprises a method of preparing new CPs that, once formed, can be heterogeneized on PMs, providing PMCs with 20 well-defined Palladium species.  The PMCs are characterized by giving rise to stable dispersions in water, they are active in catalytic processes of formation of carbon-carbon bonds in aqueous medium and in mild conditions, the superparamagnetism of the nixie ° of the particles allows their separation of the products by applying a field Magnetic, recover without degradation, can be reused by reaching very high TON values and do not undergo metallic leaching, or is insignificant, resulting in products of the catalysis with palladium contents below 10 ppm by mass (up to levels of about ppb) after the magnetic separation of the particles.  30 In a first aspect, the invention is related to new CPs that have typologies I, II and III.  35 In a second aspect, the invention is related to the synthetic methods of said CPs of types I, II and III and their precursors.  In a third aspect the invention is related to the procedures ofimmobilization of these CPs of types I, II and III on magnetic particles (PMs) of iron oxide to generate magnetic particles with the supported complexes (PMCs).  In a fourth aspect, the invention is also related to the use of said PMCs 5 as catalysts for carbon-carbon coupling reactions, and their characteristics in relation to their separation of products, their reuse, their productivity and their high resistance to degradation. and the leachate.  10 PM CP PMC DETAILED DESCRIPTION OF THE INVENTION Specifically, the invention comprises the synthesis of CPs with NHC 15 ligands substituted by complementary groups (Gc) terminal of an alkyl chain and useful for the formation of a covalent bond "Y" to the support, the post-synthetic immobilization of complexes to PMs that have a coating containing surface groups (Gs) suitable to form the "Y" anchor, and the use of these PMCs in catalysis-recovery-reuse cycles in halide activation reactions of aryl  Specifically, the CP to be supported comprises mono (NHC), bis (NHC) and bis (NHC) -chelate complexes, in which "L" is a neutral monodentate ligand L 'with donor nitrogen (type I), preferably a pyridine , and "R" is an alkyl or aryl or alkylaryl substituent, or "L" is another NHC anchor ligand with the same "R" (type II), or "L" is another NHC anchor ligand in which "R" it is a bridge alkyl chain between the two NHC ligands (type III), respectively.  In them "X" is a monoaniOnic substituent, preferably a halide, and "Gc" is a functional group capable of undergoing condensation reactions, preferably a trialkoxysilyl or primary amine, which is located at the end of an alkyl carbon chain, preferably between 1 and 4.  Particularly, in the chelate CPs (type III) the heterocyclic rings are linked through an n-link alkyl chain, preferably between 1 and 3.  7Gc NN and 'FR X-Pd-X L' Gc, opy N X-Pd-X R NN GC Pd A 'Gc "(x' X Th-Gc The PMs used in support are commercially available and characterized by 5 diameters in the range of tens to hundreds of nanOmeters, preferably 100-500 nm, for a nixie ° of an iron oxide, preferably maghemite, and for an inert coating such as silica or polystyrene functionalized with "Gs", preferably silanoles and acids carboxylic, respectively.  Additionally, the immobilization process consists of condensation reactions, preferably with formation of siloxane or amide groups, between the CPs and the corresponding PMs dispersed in organic solvents, or preferably in an aqueous medium in the presence of small amounts of non-ionic surfactants.  15 ftal, N-T.  N kin INH2NH 2 (CH3) 2CHOH N 2 PdX2 / K2CO31L 'CH2Cl2 Ag20 / = N LN / I-ZzN fta1. 14, X, A X - X- tv THF CH3CN ftall- / n tr ftal (R'0) 3Sii + X CH2Cl2 (R'0) 3S1 N.  R X-Pd-X L 'I (Si) P = 1 N -ny AgX 3 [PdX2 (L "2)] in X-Pd-X CH2Cl2 R -1 1" tNN4Gc 8 II 4 1 Pd (OAc ) 2 DMS0 NLN Pd tIal-An X / X kftal 5 NH 2 NH2I CH3CN Nk H2N45Pd n X / X (N1-12 III (A)The present invention also concerns the uses of the PMCs of the invention in carbon-carbon coupling reactions, particularly Heck-Mizoroki and Suzuki-Miyaura with aryl halides, dispersed in an accusing medium and in mild conditions, and their reuse in catalysis after its effective separation of the products by means of an external magnet.  The synthesis of some of the CPs of this invention that have formulas of types I, ll and Ill can be achieved by the transformations indicated in the previous scheme.  The especially preferred ester complexes described in the examples of this invention and the methods for preparing the complexes of the I-Ill types and their intermediates consist of: a) transforming N-substituted imizarles preferably, but not exclusively, non-substituted heterocyclic carbon in position 2, by reactions of N-15 alkylation with N- (haloalkyl) phthalimides, to form and isolate salts of imidazolium 1 with protected primary amines in the form of phthalimido (phthalic) group, 1 20 where R may be a alkyl, aryl or alkylaryl group, containing between 1 and 20 carbon atoms, and may be substituted by groups without active protons (halogen, sulfonate, carboxylate, ether, floater, ketone, sulfoxide, ester, amide, nitrile); where alternatively R may be another chain with the phthalimido group; where X-can be an aniOnic species, preferably a halide; and where the spacer between the protective group and the heterocycle is defined by a chain length of n links that can be comprised between 1 and 4 carbons.  b) N-substituted N-substituted transformer, preferably, but not exclusively, non-substituted in heterocyclic carbon at position 2, by reactions of N-30 alkylation with (haloalkyl) trialkoxysilanes, to form and isolate imidazolium salts 2 (Si) with a trialkoxysilyl group, 9(I: 110) 3 If N, R X-2 (Si) where R, X and n have been previously defined in transformation a); where alternatively R may be another chain with the trialkoxysilyl group; and where R '5 can be methyl or ethyl.  c) transform the imidazolium 1 salts, by conventional procedures of Gabriel's synthesis (acidic or basic hydrolysis), or preferably by the Ing-Manske method using hydrazine, to formerly and isolate imidazolium salts 2 (A) with a 10 Primary chain terminal amine group, F ----- H2NNN. R 2 (A) where R, X and n have been previously defined in transformation a); and where alternatively R may be another chain with a terminal primary amine.  d) transform the imidazolium 2 salts (Si), by a patented procedure (Organ, M.  G. , etal. , CA2556850A1), to form and isolate mono complexes (NHC) of type 1 (81), in which the carbine ligand is coordinated, preferably but not exclusively, by its carbon 2, 1 = 1.  (Fro) 3sii. . . ), NyN, R X -Pd- X L 'l (Si) where R, X and n have been previously defined in the transformed & a) and R' in the transformed &b); where natively the ligands X may independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxy, aryloxide, beta-diketonate, substituted or unsubstituted thiolate; and where L 'is a neutral monodentate ligand with nitrogen donor, preferably 10a pyridine that can be substituted by alkyls or halides in any of its carbons.  e) transform the imidazolium 2 salts (Si or A), by the standard procedure 5 described by Lin (Wang, H.  M.  J. , et al.  1998) with Silver Oxide, to form and isolate NHC complexes of silver 3 (Si or A), in which the carbine ligand is coordinated, preferably but not exclusively, by its carbon 2, 10 (R10) 3Si, / Ny N.  R AgX 3 (Si) H2N. 0, nNyN R AgX 3 (A) where R, X and n have been previously defined in transformation a) and R 'in transformation b).  f) transform the silver complexes 3 (Si or A), by reactions of transmetalation to palladium (ii) precursors with thousands ligands and of general formula [PdX2L "2] (L" 2 = ethylenediamine, N, N, N 'N'-tetramethylethylenediamine, 1,5-cyclooctadiene; or L "= benzonitrile, acetonitrile), to form and isolate bis (NHC) type II (Si or A) complexes, in which the carbene ligands are coordinated, preferably but not exclusively, for its carbon 2, 20 / = (R0) 3SiNyN, RX -Pd-X R 'NN / fiSi (OR') 3 II (Si) / = H2NNyN, RX -Pd- X R_Pk 'NN in NH2 11 (A) where R, X and n have been previously defined in transformed & a) and R 'in transformation b); and where alternatively the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryl oxide, beta-diketonate, substituted or unsubstituted thiolate.  g) transforming bis (imidazolyl) alkanes, preferably but not exclusively, unsubstituted in the heterocyclic carbon in position 2, to form and isolate salts of 115 imidazolium 4 with protected primary amines in the form of a phthalimide (phthalyl) group by N-alkylation reactions with N- (haloalkyl) phthalimides, n 'f NrOn (% N 0 0 4 where X- yn have been previously defined in the transformation a) and the bridge between imidazolic rings is defined by a chain length of n 'links that can be between 1 and 3.  10 h) transform salts 4, by means of metalation reactions in the presence of palladium acetate, to form and isolate bis (NHC) chelate 5 complexes with a protected primary amine in the form of a phthalimide (phtal) group, in which the carbine ligands they are coordinated, preferably but not exclusively, by their carbon 2, and I 1 — Pd) N NAn Xj 15 5 where X- yn have been previously defined in transformation a) and n 'in transformation g); and where additionally the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate i) transform chelate complexes 5, by procedures Conventional methods of Gabriel's synthesis (acidic or basic hydrolysis), or preferably by the lng-Manske method using hydrazine, to form and isolate bis (NHC) chelate complexes of type III (A) with chain-terminating main amine groups, in which the carbene ligands are coordinated, preferably but not exclusively, by their carbon 2, 12Pd H2N4j / n X / X kNH2 III (A) where X and n have been previously defined in transformation a) and n 'in transformation g); and where alternatively the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryl oxide, beta-diketonate, substituted or unsubstituted thiolate.  With regard to the synthesis of PMCs of this invention, 10 condensation reactions between the Gs of the PMs and the corresponding Gc of the CPs of types I, II or III can be achieved.  The PMs used as support are commercially available with a nude °, preferably but not limited to, of maghemite (y-Fe203) and are coated with silica or, alternatively, with polystyrene functionalized with carboxylic acid groups.  Especially preferred PMCs are described in the examples of this invention and the methods for preparing them consist of: j) heterogeneizing the CPs of types I (Si) and II (Si) on silica coated PMs, by condensing the groups trialkoxysilyl of the corresponding CPs and surface silanol groups of the PMs, to form siloxane anchors and isolate the corresponding PMC (Si) I and PMC (Si) II, [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] FeO.  [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] PMC (Yes) 1 0, O-Si N N'R 0 '1`);) and X — Pd-X L' l (Yes ) - anchored 13[Pd] [Pd] [Pd] [Pd] [Pd] [Pd] PMC (Si) II / = 0-Sid x_Ny N —0 0 (1) 'X — Pd-X FOC) - II (Yes) - anchored where R, X and n have been previously defined in transformation a) and L "in transformation d); and where alternatively the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryl oxide, beta-diketonate, substituted or unsubstituted thiolate.  The immobilization process comprises the dispersion of the PMs in organic solvents, or preferably in a hydroalcoholic medium in the presence of small amounts of non-ionic surfactants with high hydrophilic-hydrophobic balance (HLB> 15, used below their critical micellar concentration) , a slow addition of an alcoholic solution of the CP to be immobilized, a constant mechanical agitation and a washing sequence consisting of trapping the PMCs with an external magnet and separating them by decanting the solutions.  The PMC (S1) 1 and 15 PMC (S1) 11 are characterized by palladium contents that correspond to about 1-4 CP molecules immobilized per nm2 of surface.  Table 1 collects metal contents from the examples of especially preferred PMCs.  Table 1 Palladium content in the PMC (Si) I and PMC (Si) II of the examples. at PMC (Si) In ° PMC (S1) 11 n °: 1 mg Pd / g MNPs 1.27% by weight of Pd 0.28 mmol Pd / g MNPs 0.026 (Molecules / nm2) ° 1.6 2 3 1 2 3 3.59 3.07 2.39 5.07 4.25 0.77 0.66 0.24 0.51 0.43 0.072 0.062 0.022 0.048 0.040 4.3 3.7 1.3 2.9 2.4 a Determined by ICP-MS.  Relative Standard Deviations in quantifications s10%.  For PMs of 300 nm, density of 2 g / cm3 and a specific surface area of 10 m2 / g.  k) heterogeneize CPs of types II (A) and III (A) on PMs coated with 145 crosslinked polystyrene functionalized with carboxylic acid groups (density of COOH groups .  300 pmol / g), by condensing the primary amine groups of the corresponding CPs and the surface acid groups of the PMs, to form amide anchors and isolate the corresponding PMC (A) II and PMC (A) III, [Pd] [Pd] [Pd] [Pd] [Pd] H / = NN 0 X -Pd- X 0 N N. RN "n H [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] PMC (A) II [Pd] [Pd] [Pd] PMC (A) 111 [P '• [Pd] 11 ( A) - anchored NH OFIN X 'Pd (>) X /) --- N nri NH 111 (A) - anchored „,,,, 10 where R, X and n have been previously defined in transformation a) and n" in the transformation g); and where alternatively the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxy, aryloxide, beta-diketonate, substituted or unsubstituted thiolate.  15 The immobilization procedure is based on a modification of a described method (Rosario-Amorin, D. , et al.  2012) and includes the dispersion of PMs in a hydroalcoholic medium in the presence of small amounts of non-ionic surfactants with a high hydrophilic-hydrophobic balance (HLB> 15, used below their critical micellar concentration) in the presence of a carbodiimide as an agent of 20 coupling, the addition of a solution in a very polar solvent of the CP at 15immobilize, a constant mechanical agitation and a sequence of washes that consists of trapping the PMCs with an external magnet and separating them by decanting the solutions.  The PMC (A) II or PMC (A) III are characterized by palladium contents that correspond in tomb to 1-3 CP molecules immobilized per nm2 of 5 surface.  Table 2 collects metal contents from the examples of especially preferred PMCs.  Table 2.  Palladium content in the PMC (A) II and PMC (A) III of the examples. a mg Pd / g MNPs ° A by weight of Pd mmol Pd / 9 MNPs (Molecules / nm2) ° PMC (A) IIn ° PMC (A) IIIn ° No: 1 2 3 4 2.58 5.38 3, 60 8.12 0.26 0.54 0.36 0.81 0.024 0.046 0.031 0.076 1.0 1.8 1.6 3.1 a Determined by ICP-MS.  Relative Standard Deviations in quantifications s10%.  For PMs of 200 nm, density of 2 g / cm3 and a specific surface area of 15 m2 / g.  The essential characteristics of the PMCs of the present invention are that they catalyze 10 carbon-carbon coupling reactions under mild conditions, which are easily separated from the reaction medium, which can be reused in a series of numerous recycled ones, which are very robust to degradation. and that they hardly suffer leaching of palladium.  An exhaustive evaluation of the catalytic capacities of the PMCs of the present invention focused, but not limited to model reactions of 15 Heck-Mizoroki and Suzuki-Miyaura with aryl halides, with which their kinetic profiles have been analyzed ( % conversion vs.  time), its recyclability in successive catalysis-recovery-reuse tests, the maintenance of its properties in the recycling series and the leachate suffered by the PMCs in the mines.  Below is a selection of results, the procedures used are described in examples 20 of this invention and the evaluation of the catalytic properties consists in: I) testing the PMCs of this invention in Suzuki-Miyaura reactions between an arylboronic acid, preferably phenylboronic acid, with aryl halides, preferably 4-bromo- and 4-chlorotoluene, at a mild temperature (65-80 ° C), in a mechanically stirred aqueous organic medium at constant speed in the presence of small amounts of surfactants non-ionic with high hydrophilic-hydrophobic balance (HLB> 15, used below its critical level of concentration) and with low loads of 16palladium (0.024-0.050 mol% [Pd], with respect to the corresponding haloarene used as the limiting substrate).  Table 3 collects the results obtained with especially preferred PMCs.  Table 3 Results in the Suzuki-Miyaura reaction with the PMCs in the examples.  substrate precursor input medium D T (° C) t (h) conversion (%) to ld PMC (Yes) I1 PMC (Yes) I2 PMC (Si) I2 PMC (S1) 13 PMC (Yes) 12 PMC (Yes) I3 4 -bromotoluene 4-bromotoluene 4-bromotoluene 4-bromotoluene 4-chlorotoluene 4-chlorotoluene Tx / Et0H Tx / Et0H Tx / THF Tx / Et0H Tx / Et0H Tx / Et0H 65 65 65 65 80 80 2 2 2 2 5 5 70 92 50 85 80 76 PMC (Si) I11 4-bromotoluene Tx / THF 65 15 86 PMC (S1) 112 4-bromotoluene Tx / THF 65 15 100 PMC (Si) I13 4-bromotoluene Tx / THF 65 15 100 2e'f PMC ( S1) 111 4-chlorotoluene Tx / THF 80 30 51 PMC (S1) 112 4-chlorotoluene Tx / THF 80 30 77 PMC (S1) 113 4-chlorotoluene Tx / THF 80 30 68 PMC (A) I11 4-bromotoluene Tx / THF 65 15 91 PMC (A) II2 4-bromotoluene Tx / THF 65 15 100 3e, f PMC (A) II3 4-bromotoluene TilTHF 65 15 100 PMC (S1) 111 4-chlorotoluene Tx / THF 80 30 56 PMC (A ) II2 4-chlorotoluene Tx / THF 80 30 82 PMC (A) II3 4-chlorotoluene Tx / THF 80 30 72 PMC (A) III4 4-bromotoluene Tx / THF 65 20 100 4e'f PMC (A) III4 4-chlorotoluene Tx / THF 80 48 100 Against phenylboronic acid.  Tx / Et0H (1: 4), Tx / THF (9: 1).  Tx = solution of Trit & in "X405 in water to Determined by gas chromatography with FID detector.  Reproducibility ± 3%.  Metal load: 0.05 mol% [Pd].  e Metal load: 0.024 mol% [Pd].  f Total conversion at 30 h with 4-bromotoluene with PMC (S1) 111 and PMC (A) 111, at 82 h with 4-chlorotoluene with PMC (Si) 112 y3 and PMC (A) I13 and 3, and at 90 hours with the PMC (Si) 111 and PMC (A) II.  5 m) test the PMCs of this invention in Heck-Mizoroki reactions between an olefin, preferably an acrylate with aryl halides, preferably 4- iodotoluene, at a mild temperature (5 90 ° C), in a stirred organic-aqueous medium mechanically at constant speed () in the presence of small amounts of 10 non-ionic surfactants with high hydrophilic-hydrophobic balance (HLB> 15, used by 17below its critical micellar concentration) and with low palladium loads (0.024-0.050 mol% [Pd], with respect to the haloarene used as the limiting substrate).  Table 4 shows the results obtained with the especially preferred PMCs.  Table 4  Results in the Heck-Mizoroki reaction with the PMCs in the examples.  substrate precursor input medium D T (° C) t (h) Conversion (%) to PMC (S1) 11 4-iodotoluene Tx / THF 90 8 100 1d PMC (Si) I2 4-iodotoluene Tx / THF 90 6 100 PMC (Si ) I3 4-iodotoluene Tx / THF 90 7 100 PMC (Si) 111 4-iodotoluene Tx / THF 90 20 100 2e PMC (Si) 112 4-iodotoluene Tx / THE 90 12 100 PMC (Si) 113 4-iodotoluene Tx / THF 90 15 100 PMC (A) II1 4-iodotoluene Tx / THF 90 20 100 3e PMC (A) II2 4-iodotoluene Tx / THF 90 10 100 PMC (A) II3 4-iodotoluene TX / THE 90 15 100 4e PMC ( A) III4 4-iodotoluene Tx / THF 90 15 100 a Against methyl acrylate.  Tx / THF (9: 1).  Tx = solution of TritOnTM X405 in water Determined by gas chromatography with FID detector.  Reproducibility ± 3%.  d Metal load: 0.05 mol% [Pd].  ° Metallic carp: 0.024 mol% [Pd].  5 n) evaluate the recyclability of the PMCs of this invention, by means of the separation-washing-reuse sequence, in the Suzuki-Miyaura reactions that have been defined previously in the activity tests l), comparing the kinetic profiles of the successive reactions of each series of recycled.  Specifically, there have been twelve successive recycling of each catalyst (13 uses counting the initial reaction or recycling numbered 0) by separating the PMCs using an external magnet and decanting the solutions.  A selection of graphic representations of some profiles for some of the especially preferred PMCs is as follows: 15 Profile of the initial Suzuki-Miyaura reaction (0) and of the first (1), second (2) recycled ones and twelfth (12) for PMC (S1) 112 with: a) 4-bromotoluene and b) 4- chlorotoluene: 1880 c 60: or> 40 20 (0) (1) (2) (12) 3 6 15 0 5 10 15 20 25 Reaction time (h) 30 Initial Suzuki-Miyaura reaction profile (0) and of recycled first (1), second (2) and twelfth (12) for PMC (A) II3 with: a) 4-bromotoluene and b) 4- 5 chlorotoluene: 3 6 9 12 15 Reaction time (h) b) 100 .  0 5 10 15 20 25 Reaction time (h) 30 Reaction profile of initial Suzuki-Miyaura (0) and recycled first (1), second (2) and twelfth (12) for PMC (A) III4 with : a) 4-bromotoluene and b) 4- 10 chlorotoluene: a) loo 80 60 40 20 5 10 15 20 Reaction time (h) 19 b) loo 80 C 60 1. 0 8 16 24 Reaction time (h) 32 40 48o) evaluate the recyclability of the PMCs of this invention, by means of the separation-washes-reuse sequence, in the Heck-Mizoroki reactions that have been previously defined in the activity tests m), comparing the kinetic profiles of the successive reactions of each series of recycled.  Specifically, there have been twelve successive recycles of each catalyst (13 uses counting the initial reaction or recycling numbered 0) separating the PMCs using an external magnet and decanting the solutions.  A selection of graphical representations of some profiles for some of the especially preferred PMCs, is the one shown below: 15 Profile of the initial Heck-Mizoroki reaction (0) and the recycled first (1), second (2) ) and twelfth (12) with 4-iodotoluene for: a) PMC (S1) 13 and b) PMC (S1) 112: 1 2 3 4 5 6 7 Reaction time (h) 2 4 6 8 10 Reaction time (h ) 12 Profile of the initial Heck-Mizoroki reaction (0) and recycled first (1), second (2) and twelfth (12) PMC (A) II14: a) 100 (2) 80 with 4-iodotoluene for : a) PMC (A) II3 and b) 5 10 Reacciem time (h). 5 20 5 10 Reaction time (h) 15p) quantify the possible leaching of palladium from the PMCs of this invention, by quantitative elementary analysis of palladium (ICP-MS), both of the separate solutions in each consecutive use and of the PMCs at the end of each series of 5 recycled in the Suzuki-Miyaura reactions that have been previously defined in the activity tests l), correlating the eventual leachate of the PMCs with the slight decreases in the conversions (measured in each case always at the same time) in the successive reactions in each series of the trials defined above in the evaluation n).  Table 5 shows an illustrative selection 10 of these correlations in this type of coupling for some of the especially preferred PMCs.  Table 5.  Conversion drop and leaching of palladium in the recycled, and total% of the metal found in the solutions and lost by the PMCs in Suzuki-Miyaura reactions.  recycled precursor N °: 0-1 1. 2 2-3 3-11 12 total lost by the PMCe decrease in PMC (Si) 112` conver.  in% at 0 I) 0 9 2 11% Pd leachateb 1.2 0.0 0.2 7.2 0.4 9 n. d.  PMC descent (Si) 112d conver.  in% at 5 0 0 11 1 17% Pd leachateb 3.8 0.5 0.3 13.0 0.4 18 19 decrease in PMC (A) I13c conver.  in ° / 08 0 0 0 7 3 10% Pd leachateb 0.0 0.0 0.0 6.4 2.6 9 8 decrease in PMC (A) I13d conver.  in% at 3 0 0 8 2 13% Pd leachateb 4.6 0 0 6.8 2.6 14 n. d.  decrease in PMC (A) II14c conver.  in% at 0 0 0 0 0 0% Pd leachateb 0.0 0.0 0.0 0.2 0.0 0.2 n. d.  decrease in PMC (A) II14d conver.  in% at 0 0 0 4 5 9% Pd leachateb 0.1 0.1 0.0 0.5 0.2 0.9 1.5 a Determined by gas chromatography with FID deletor.  Reproduability ± 3%.  b Determined by Relative Standard Deviations in quantifications 5 10%.  With 4-bromotoluene; measured at 15 h for PMC (Si) 112 and PMC (A) II3, and at 20 h for PMC (A) II14.  twenty-one° With 4-chlorotoluene; measured at 30 h for PMC (S1) 112 and PMC (A) II3, and at 48 h for PMC (A) II14.  e Measured by ICP-MS on the PMCs themselves after thirteen uses; n. d.  = Not determined.  q) quantify the possible leaching of palladium from the PMCs of this invention, by quantitative elementary analysis of palladium (ICP-MS), both of the separate solutions in each consecutive use and of the PMCs at the end of each series of 5 recycled in the reactions of Heck-Mizoroky that have been previously defined in the activity tests m), correlating the eventual leachate of the PMCs with the slight decreases in the conversions (measured in each case always at the same time) in the successive reactions in each series of the tests that have been previously defined in the evaluation o).  Table 6 shows an illustrative selection 10 of these correlations in this type of coupling for some of the especially preferred PMCs.  Table 6.  Reduction of conversion and leaching of palladium in the recycled, and total% of the metal found in the solutions and lost by the PMCs in Heck-Mizoroky reactions.  a Determined lost by recycled precursor N °: 0-1 1-2 2-3 3-11 12 total PMCs d decrease in PMC (Si) 13b conver.  in% at 0 0 0 9 2 11% Pd leachate 1.9 0.9 0.9 8.0 1.3 13 n. d.  PMC descent (Si) 112c conver.  in% at 0 0 0 8 1 9% Pd leachateb 0.8 0.0 0.2 6.9 1.1 9 11 decrease in PMC (A) I13c conver.  in% at 0 0 0 4 1 5% Pd leachateb 0.5 0.3 0.1 3.1 1.0 5 7 decrease in PMC (A) 1114` conver.  in% at 0 0 0 0 0 0% Pd leachateb 0.0 0.0 0.0 0.02 0.0 0.02 0.18 pair gas chromatography with FID detector.  Reproducibility ± 3%.  b Determined by ICP-MS.  Standard Relative Deviations in quantifications s 10%.  Measures at 7 o'clock for PMC (Si) I3, at 12 o'clock stop PMC (Si) 112 and at 15 o'clock for PMC (A) II3 and PMC (A) II14.  d Measured by ICP-MS on the PMCs themselves after thirteen uses; n. d.  = Not determined °.  r) determine the productivity (TON ° or "turnover number" in the first use of the catalyst) and activity (TOF0 or "turnover frequency" in the first use of the 22catalyst) of the PMCs of this invention in the initial Suzuki-Miyaura reactions that have been previously defined in the activity tests I), as well as the accumulated TON (TONT) and the average TOF (TOFAv) in each series of consecutive uses which have been described previously in the evaluation n), together with the palladium content found in the products whose determination is described in the quantifications p).  Table 7 and Table 8 collect the values found in the Suzuki-Miyaura reactions for some of the especially preferred PMCs of this invention.  10 Table 7.  TOF and TON values shown for some PMCs of the examples in the Suzuki-Miyaura reaction with 4-bromotoluene and the metal content found in the products.  TON TOFAv TON— TOFA ,, Precursor content TONob TONTG (hl) b 01-1) c (11-1) Pd (ppm) d PMC (Si) 111 3584 239 42128 216 23 3 PMC (Yes) 112 4167 278 52046 267 11 1 PMC (Yes) 113 4167 278 52088 267 11 2 PMC (A) II1 3792 253 43624 224 29 3 PMC (A) 1I2 4167 278 53046 272 6 1 PMC (A) 113 4167 278 52629 270 9 1 PMC (A) 1114 4167 208 53879 207 1 0.023 a Reaction times: 20 h for PMC (A) III4, 15 h for the rest Value in the initial reaction.  Value in the thirteen uses of the catalyst.  d Palladium contamination of the product in parts per milk: 0 by mass.  Table 8  TOF and TON values shown for some PMCs of the examples in the Suzuki-Miyaura reaction with 4-chlorotoluene and the metal content found in the products.  TON TOFAv TON - TOFA, Precursor content TONob TONT` (11-1) b (h-1) `(h-1) Pd (ppm) d PMC (Si) I11 2125 71 22085 57 14 10 PMC (Yes) 112 3209 107 3650: 3 94 13 3 PMC (S1) 113 2834 94 32128 82 12 3 PMC (A) II1 2334 78 25210 65 13 7 PMC (A) I12 3417 114 39211 101 13 2 PMC (A) I13 3042 101 36545 94 7 2 PMC (A) 1114 4167 87 53254 85 2 0.107 23a Reaction times: 48 h for PMC (A) III4, 30 h for the rest b Value in the initial reaction.  Value in the thirteen uses of the catalyst.  d Contamination by product palladium in parts per million in mass.  s) determine the productivity (TON () or "turnover number" in the first use of the catalyst) and activity (TOF0 or 'turnover frequency "in the first use of the catalyst) values of the PMCs of this invention in the initial reactions of Heck-5 Mizoroki that have been previously defined in the m) activity tests, as well as the accumulated TON (TONT) and the average TOF (TOFA,) in each series of consecutive uses that have been previously described in the evaluation), together with the palladium content found in the products whose determination is described in the quantifications q).  Table 9 collects the values found in Heck-Mizoroki reactions 10 for the PMCs of the examples of this invention.  Table 9  TOF and TON values shown by the PMCs of the examples in the Heck-Mizoroki reaction with 4-iodotoluene and the metal content found in the products.  precursor TONob TON (11-1) b TONT` TOFAv (h-1) `TOF0 - TOFA, (11-1) Pd content (ppm) d PMC (S1) 11 2000 250 24400 235 15 5 PMC (Yes) I2 2000 333 25 100 322 11 4 PMC (S1) 13 2000 286 25260 278 8 3 PMC (Yes) II1 4167 208 52421 202 6 2 PMC (Yes) 112 4167 347 52963 340 7 1 PMC (Yes) 113 4167 278 53254 273 5 1 PMC (A) II1 4167 208 52921 204 4 2 PMC (A) 112 4167 417 53463 411 6 1 PMC (A) 1I3 4167 278 53504 274 4 1 PMC (A) 1I14 4167 278 53963 277 1 0.002 Reaction times: 8 (PMC (Yes) 11), 6 (PMC (Si) 12), 7 (PMC (Si) 13), 20 (PMC (S0111 and PMC (A) II1), 12 (PMC (Si) I12), 10 (PMC ( A) I12) and 15 h (PMC (Si) I13, PMC (A) II3 and PMC (A) II14.  b Value in the initial reaction.  Value in the thirteen uses of the catalyst.  d Contamination by product palladium in parts per million.  t) additionally and finally, analyze the TEM (Electron Microscopy of 15 Transmission) images of the PMCs, both before their use in the reactions that have occurred.defined above in the activity tests I) and m) as at the end of the series of recycles that have been previously defined in the evaluations n) i), as well as samples prepared from the separate solutions in each reaction, verifying that the PMCs they do not undergo appreciable morphological changes and that no aggregates of metallic palladium are observed next to them or in the samples prepared from the solutions separated with the products at the end of each reaction.  10 15 DESCRIPTION OF THE DRAWINGS Figure 1.  Schematic representation of the heterogeneization of the CPs to give the PMCs object of the present invention.  Figure 2  Schematic representation of the CPs object of the present invention.  Figure 3  Synthesis scheme of the new CPs of types I, II and III and their precursors.  Figure 4  Profile of the initial Suzuki-Miyaura (0) and recycled first 20 (1), second (2) and twelfth (12) for PMC (S1) 112 with: a) 4-bromotoluene and b) 4-chlorotoluene.  Figure 5  Profile of the initial Suzuki-Miyaura reaction (0) and the first (1), second (2) and twelfth (12) recycled ones for PMC (A) II3 with: a) 4-bromotoluene and b) 25 4-chlorotoluene.  30 Figure 6.  Profile of the initial Suzuki-Miyaura reaction (0) and the first (1), second (2) and twelfth (12) recycled ones for PMC (A) III4 with: a) 4-bromotoluene and b) 4-chlorotoluene.  Figure 7  Profile of the initial Heck-Mizoroki (0) and recycled first (1), second (2) and twelfth (12) reactions with 4-iodotoluene for: a) PMC (S1) 13 and b) PMC (S1) 112 .  35 Figure 8.  Profile of the initial Heck-Mizoroki (0) and recycled first (1), second (2) and twelfth (12) reactions with 4-iodotoluene for: a) PMC (A) II3 and b) 25PMC (A) II14.  MODE OF EMBODIMENT OF THE INVENTION 5 The present invention is further illustrated by the following illustrative examples, although not limiting, in which experimental procedures, spectroscopic and analytical data of palladium complexes and their precursors and magnetic particles with the complexes are indicated. supported, as well as catalytic tests with them.  Example 1.  Preparation of the imidazolium salt 1. one.  In a 100 mL ampoule, equipped with a tefle punzem valve, n, N-15 methylimidazole (0.65 g, 7.8 mmol) and N- (2-Bromoethyl) phthalimide (1.00 g, 3.9 mmol), in about 40 mL of THF and heated with stirring to 80 ° C.  After 16 h, the presence of a white precipitate was observed which, after filtering, was washed) with hexane (2 x 10 mL) to remove excess N-methylimidazole and dried) under vacuum.  Product 1 was obtained. 1 as a white solid (1.18 g, 90%).  Anal.  Calc.  for C14H1402N3Br. H20 (354.20): C, 47.47; H, 4.55; N, 20 11.86%.  Found: C, 47.42; H, 4.24; N, 11.93%.  1H NMR (CDCI3, 300 MHz): ô4.06 (s, 3H, Imz-Me), 4.23 (t, 3. 4th = 5.4 Hz, 2H, CH2ftal), 4.79 (t, 34, H = 5.4 Hz, 2H, CH2Innz), 7.25 and 7.26 (2 xs, 2 x 1H, Imz-H4y H5), 7.73 (m, 2H, o-ftal), 7.80 (m, 2H, m-ftal), 10.57 (s, 1H, Imz-H2).  13C NMR {1H} (CDCI3, 75 MHz): 6 35.3 (CH2ftal), 37.5 (lmz-Me), 47.4 (CH2Imz), 122.4 and 123.1 (Imz-C4 and C5) , 122.7 (o-ftal), 131.0 (ipso-ftal), 134.1 (m-ftal), 136.6 (Imz-C2), 167.27.2 (C = 0).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 256.1092 [M-Br].  30 1. 1 Example 2.  Preparation of the imidazolium salt 1. 2.  Compound 1. 2 be prepared) similar to that described for salt 1. 1 of Example 1, starting with N-mesitylimidazole (0.50 g, 2.7 mmol) and N- (2-bromoethyl) phthalimide (0.34 g, 1.4 26mmol), in THF (40 mL), at 90 ° C and for 16 h.  Compound 1 was obtained. 2 eat a white oiled solid (0.56 g, 95%).  Anal.  Calc.  for C22H2202N3Br (440.34): C, 60.01; H, 5.04; N, 9.54%.  Found: C, 59.75; H, 5.06; N, 9.47%.  1H NMR (CDCI3, 300 MHz): 6 2.09 (s, 6H, Month-o-Me), 2.31 (s, 3H, Month-p-Me), 4.33 (t, JH, H = 5.0 Hz, 2H, 5 CH2ftal), 5.14 (t, 34, H = 5.0 Hz, 2H, CH2Imz), 6.97 (s, 2H, m-Month), 7.04 and 7, 51 (2 xt, = 1.9 Hz, 2 x 1H, Imz-H4 and H5), 7.73 (m, 2H, o-ftal), 7.78 (m, 2H, m-ftal), 10, 50 (t, 3JH, H = 1.9 Hz, 1H, Imz-H2).  13C NMR {1H} (CDCI3, 75 MHz): 617.6 (Month-p-Me), 21.1 (Month-o-Me), 39.0 (CH2ftal), 49.6 (CH2Imz), 122, 8 and 123.0 (Imz-C4 and C5), 123.7 (o-ftal), 129.9 (m-Month), 130.6 (ipso-Month), 131.5 (ipso-ftal), 134 , 4 (o-Month), 134.5 (m-ftal), 138.8 (Imz-C2), 141.4 (p-10 Month), 167.2 (C = 0).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NR4HCOO): m / z 360.1711 [M-Br].  one. 2 15 Example 3.  Preparation of the imidazolium salt 1. 3.  Compound 1. 3 was prepared similarly to that described for salt 1. 1 of Example 1, starting with N- (2,6-diisopropylphenyl) imidazole (0.50 g, 2.2 mmol) and N- (2-bromoethyl) phthalimide (0.28 g, 1.1 mmol), in THF (40 mL), at 90 ° C and for 16 h.  Compound 1 was obtained. 3 20 as an oily white solid (0.48 g, 90%).  Anal.  Cale.  for C25H2802N3Br. 1.2H20 (505.04): C, 59.57; H, 6.08; N, 8.34%.  Found: C, 59.96; H, 5.95; N, 7.92%.  1H NMR (CDCI3, 300 MHz): 61.11 (d, 34, H = 7.0 Hz, 6H, CH (CH3) 2), 1.23 (d, JH, H = 7.0 Hz, 6H, CH (CH3) 2), 1.83 (Sep, 3JH, H = 7.0 Hz, 2H, CH (CH3) 2), 4.35 (t, 3JH, H = 5.2 Hz, 2H, CH2ftal) , 5.22 (t, 3JKH = 5.2 Hz, 2H, CH2Imz), 7.03 and 7.58 (2 xs, 2 x 1H, Imz-H4 and H5), 7.04 (d, 25 = 7 , 9 Hz, 2H, m-Ph), 7.51 (t, JH, H = 7.9 Hz, 1H, p-Ph), 7.73 (m, 2H, o-ftal), 7.80 ( m, 2H, m-ftal), 10.51 (broad s, 1H, Imz-H2).  13C NMR {1H} (CDCI3, 75 MHz): 6 24.3 (CH (CH3) 2), 24.5 (CH (CH3) 2), 28.5 (CH (CH3) 2), 39.2 ( CH2ftal), 49.7 (CH2Imz), 123.0 and 123.8 (Imz-C4 and C5), 123.6 (m-Ph), 124.7 (o-ftal), 130.1 (ipso-Ph ), 131.6 (ipso-ftal), 131.9 (o-Ph), 134.5 (m-ftal), 138.9 (Imz-C2), 145.5 (p-Ph), 167.7 (C = 0).  MS (ESI + / TOF, CH2C12 / Me0H / 5 mM NH4HCOO 30): miz 402.2176 [M-Br].  270 1c Example 4.  Preparation of the imidazolium salt 2 (51) 1.  In a 50 mL ampoule with (3-bromopropyl) triethoxysilane (0.29 g, 1.0 mmol), it was emptied for 10 min and 2 mL of dry CH3CN was added.  Then N-methylimidazole (0.08 g, 1.0 mmol) was added.  The resulting yellow solution was left under stirring at 100 ° C for 16 h, then evaporated the solvent.  The resulting yellow oil was washed with hexane (2 x 15 mL), obtaining compound 2 (51) 1 as a yellow oil (0.33 g, 89%).  Anal.  Calc.  for C13H2703N2SiBr (367.36): C, 42.50; H, 7.41; N, 7.62%.  Found: C, 42.00; H, 6.85; N, 8.04%.  1H NMR (CDCI3, 300 MHz): 6 0.52 (t, = 8.5 Hz, 2H, SiCH2), 1.12 (t, 3s / H, H = 7.0 Hz, 9H, CH3CH20), 1 , 93 (m, 2H, SiCH2CH2), 3.72 (c, 3JH, H = 7.0 Hz, 6H, CH3CH20), 4.04 (s, 3H, lmz-Me), 4.24 (t, 3AH = 7.2 Hz, 2H, CH2Imz), 7.31 and 7.57 (2 xt, 341, H = 1.6 Hz, 2 x 1H, Imz-H4 and H5), 10.2 (s, 1H, Imz-H2).  13 C NMR {1H} (CDCI3, 75 MHz): 6 7.0 (SiCH2), 18.2 (CH3CH20), 24.3 (S1CH2CH2), 36.6 (lmz-Me), 51.6 (CH2Imz) , 58.5 (CH3CH20), 121.7 and 123.5 (Imz-C4 and C5), 137.4 (Imz-C2).  MS (ESIF / TOF, CH2C12 / Me0H / 5 mM NH4HCOO): tniz 247.1780 [M-Br].  20 Br-2 (Yes) 1 Example 5.  Preparation of the imidazolium salt 2 (Si) 2.  Compound 2 (51) 2 was prepared in a manner similar to that described for salt 2 (51) 1 of Example 4, starting with N-mesitylimidazole (0.22 g, 1.2 mnnol) and the brominated derivative (0, 34 25 g, 1.2 mmol), in CH3CN (2.5 mL), at 100 ° C and for 24 h.  All solid reagents were previously held in vacuo for 10 min.  Compound 2 (51) 2 was obtained as an oiled white solid (0.55 g, 98%).  Anal.  Calc.  for C211-13503N2SiBr. 0.1H20 (489,530): C, 53.29; H, 7.50; N, 5.92%.  Found: C, 52.77; H, 7.12; N, 6.46%.  1H NMR (CDCI3, 300 MHz): 60.62 (m, 2H, SiCH2), 1.18 (t, 3 JitH = 7.0 Hz, 9H, CH3CH20), 2.04 (s, 286H, Month-o-Me), 2.07 (m, 2H, SiCH2CH2), 2.30 (s, 3H, Month-p-Me), 3.80 (c, 3JH, H = 7.0 Hz, 6H, CH3CH20), 4.72 (t, 3JH, H = 7.0 Hz, 2H, CH2Imz), 6.96 (s, 2H, m-Month), 7.15 and 7.67 (2 xt, 34 , H = 1.5 Hz, 2 x 1H, Imz-H4 and H5), 10.4 (wide s, 1H, Imz-H2).  13C NMR {1H} (CDCI3, 75 MHz): 6 6.8 (SiCH2), 17.6 (Month-o-Me), 18.2 (CH3CH20), 21.0 (Month-p-Me), 24 , 5 5 (S1CH2CH2), 52.0 (CH2Imz), 58.6 (CH3CH20), 122.7 and 122.9 (Imz-C4y C5), 129.8 (m-Month), 130.6 (ipso- Month), 134.1 (o-Month), 138.2 (Imz-C4), 141.2 (p-Month).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 391.2412 [M-Br].  10 (Et0) 3 Yes. ,, N • It • N Br-2 (Yes) 2 Example 6.  Preparation of the imidazolium salt 2 (Si) 3.  Compound 2 (S1) 3 was prepared similarly to that described for salt 2 (Si) 1 of Example 4, starting from N- (2,6-diisopropylphenyl) imidazole (0.28 g, 1.2 mmol) and the brominated derivative (0.34 g, 1.2 mmol), in CH3CN (2.5 mL), at 100 ° C and for 24 h.  All solid reagents were emptied for 10 min before use.  Compound 2 (Si) 3 was obtained as a white solid of oily appearance (0.61 g, 99%).  Anal.  Calc.  for C24H4103N2SiBr- (2.4CH3CN and 2C3H60) (728.28): C, 57.52; H, 8.03; N, 7.62%.  Found: C, 57.91; H, 8.03; N, 7.27%.  1H NMR (CDCI3, 300 MHz): ô0.61 (t, 3JKH = 7.7 20 Hz, 2H, S1CH2), 1.13 (d, 3JH, H = 7.2 Hz, 6H, CH (CH3) 2 ), 1.18 (t, 3JH, H = 7.0 Hz, 9H, CH3CH20), 1.20 (d, 34, H = 7.2 Hz, 6H, CH (CH3) 2), 2.07 ( m, 3JH, H = 7.7 Hz, 2H SiCH2CH2), 2.25 (Sep, 3JH, H = 7.2 Hz, 6H, CH (CH3) 2), 3.78 (c, 3JH, H = 7 , 0 Hz, 6H, CH3CH20), 4.78 (t, 3.41, H = 7.7 Hz, 2H, CH2Imz), 7.18 and 7.88 (2 xs wide, 2 x 1H, Imz-H4 and H5), 7.27 (d, 2H, 34H = 7.6 Hz, m-Ph), 7.49 (t, 1H, 3JH, H = 7.6 Hz, p-Ph), 10.3 ( s, 1H, Imz-H2).  13C NMR {1H} 25 (CDCI3, 75 MHz): 6 6.6 (SiCH2), 18.2 (CH3CH20), 24.0 (CH (CH3) 2), 24.3 (CH (CH3) 2), 24.5 (S1CH2CH2), 28.6 (CH (CH3) 2), 52.0 (CH2Imz), 58.5 (CH3CH20), 123.0 and 124.0 (Imz-C4 and C5), 124.6 (m-Ph), 130.0 (ipso-Ph), 131.8 (C6H3 (o-Ph), 138.2 (Imz-C2), 145.2 (p-Ph).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): miz 433.2881 [M-292 (Yes) 3 Example 7.  Preparation of the imidazolium salt 2 (A) 1.  5) Hydrazine (2.10 mL, 43.1 mmol) is added to a 50 mL vial with imidazolium 1 salt. 1 described in Example 1 (1.40 g, 4.3 mmol) in 25 mL of 2-propanol and heated at 40 ° C overnight.  The initial white suspension is taken) at a clear solution with the progress of the reaction to finally precipitate a white solid that corresponds to the by-product of the deprotection, phthalylhydrazine.  The mixture was cooled, filtered and evaporated to obtain the desired product 2 (A) 1 as a yellow oil (0.80 g, 95%).  Anal.  Calc.  for C6H12N2Br (206.08): C, 34.97; H, 5.87; N, 20.39%; Found: C, 34.31; H, 5.98; N, 19.89%.  1H NMR (CDCI3, 300 MHz): ö 3.19 (t, 3J11, H = 5.6 Hz, 2H, NH2CH2), 4.05 (s, 3H, lmz-Me), 4.44 (t, 3 , 40. 1 = 5.6 Hz, 2H, CH2Imz), 7.27 and 7.49 (2 x s, 2 x 1H, Imz-H4 and H5), 10.33 (s, 1H, Imz-H2).  13C NMR {1H} (CDCI3, 75 MHz): 6 15 36.7 (NH2CH2), 41.4 (lmz-Me), 52.3 (CH2Imz), 122.3 and 122.5 (Imz-C4 and C5 ), 138.6 (Imz-C2).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): miz 126,1026 [M-Br].  m Br-2 (A) 1 20 Example 8.  Preparation of the imidazolium salt 2 (A) 2.  Compound 2 (A) 2 is prepared) in a manner similar to that described for salt 2 (A) 1 of Example 7, starting from imidazolium salt 1. 2 described in Example 2 (1.29 g, 2.9 mmol) and hydrazine (1.43 mL, 29.0 mmol), in isopropanol, at 40 ° C and overnight.  After filtering, evaporating and washing with hexane, the imidazolium salt 2 (A) 2 was obtained as a yellow oil (0.87 g, 95%).  Anal.  Calc.  for C14H20N3Br. 0.7H20 (322.84): C, 52.08; H, 6.68; N, 13.02%; Found: C, 51.82; H, 6.34; N, 13.24%.  1H NMR (CDCI3, 300 MHz): 6 2.05 (s, 6H, Month-o-Me), 2.31 (s, 3H, Month-p-Me), 3.23 (t, 3JH, H = 5.6 Hz, 2H, NH2CH2), 4.81 (t, 3JKH = 5.6 Hz, 2H, CH2Imz), 6.97 (s, 2H, in-Month), 7.11 and 7.91 (2 xt, 3JH, H = 1.7 Hz, 2 x 305 1H, Imz-H4 and H5), 10.09 (t, 34, H = 1.7 Hz, 1H, Imz-H2).  13C NMR {1H} (CDCI3, 75 MHz): 6 17.8 (Month-p-Me), 21.0 (Month-o-Me), 40.9 (NH2CH2), 50.3 (CH2Imz), 123 , 0 and 124.0 (Imz-C4 and C5), 129.7 (m-Month), 130.7 (ipso-Month), 134.4 (o-Month), 137.9 (Imz-C2), 141.0 (p-Month).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4FICOO): m / z 230.1652 [M-H2NZ2N Br 2 (A) 2 Example 9.  Preparation of the imidazolium salt 2 (A) 3.  Compound 2 (A) 3 was prepared similarly to that described for salt 2 (A) 1 of Example 7, starting from imidazolium salt 1. 3 described in Example 3 (0.46 mL, 9.50 mmol) and hydrazine (0.46 mL, 9.50 mmol), in isopropanol, at 40 ° C and overnight.  After filtering, evaporating and washing with hexane, the imidazolium 2 (A) 2 salt was obtained as a yellow oil (0.31 g, 92%).  Anal.  Calc.  for C17H26N3Br-0.4H20: C, 56.79; H, 7.51; N, 11.69%; Found: C, 57.07; H, 7.98; N, 12.13%.  1H NMR (CDCI3, 300 MHz): (51.17 (d, 3JKH = 6.9 Hz, 12H, CH (CH3) 2), 2.31 (Sep. , 34H = 6.9 Hz, 2H, CH (CH3) 2), 3.22 (t, 34H = 5.4 Hz, 2H, NH2CH2), 4.87 (t, 34tH = 5.4 Hz, 2H, CH2Imz), 7.12 and 7.58 (2 xt, 3.41, H = 1.3 Hz, 2 x 1H, Imz-H4 and H5), 7.28 (d, 3. 41, H = 7.9 Hz, 2H, m-Ph), 7.52 (t, 3JKH = 7.9 Hz, 1H, p-Ph), 10.51 (t, 3JKH = 1.3 Hz, 1H , Imz-H2).  13C NMR {1H} (CDCI3, 75 MHz): (5 24.1 20 (CH (CH3) 2), 24.4 (CH (CH3) 2), 28.6 (CH (CH3) 2), 41, 6 (NH2CH2), 51.6 (CH2Imz), 123.2 and 123.5 (Imz-C4 and C5), 124.7 (m-Ph), 130.1 (ipso-Ph), 131.9 (or -Ph), 139.0 (Imz-C2), 145.5 (p-Ph).  MS (ESIIITOF, CH2C12 / Me0H / 5 mM NH4HCOO): m / z 272,2082 [M-Br].  25 2 (A) 3 Example 10.  Preparation of the palladium complex l (Si) 1.  The imidazolium 2 (Si) 1 salt described in Example 4 (0.58 g, 1.6 mmol), palladium chloride (0.28 g, 1.6 mmol), carbonate carbonate were weighed under an argon under argon. potassium (1.09 g, 317.9 mmol) and sodium iodide (1.66 g, 11.1 mmol), and placed in a Buchi desiccator at 10 mbar and 95 ° C for 24 h.  Subsequently, 12 mL of 4-picoline was added, previously treated with shieve molecules overnight, forming a reddish suspension that was allowed to stir at 80 ° C for 24 hours under argon.  After evaporating the 4-picoline, 5 was extracted with CHCI3, the solution was filtered and hexane was added to remove palladium halide residues.  After filtering and evaporating the solvent, complex 1 (Si) I was obtained as a yellow powdery solid (1.12 g, 96%).  Anal.  Calc.  for C19H3303N312S1Pd (739.80): C, 30.85; H, 4.50; N, 5.68%.  Found: C, 30.36; H, 4.40; N, 5.93%.  1H NMR (CDCI3, 300 MHz): 6 0.73 (t, 3JH, H = 8.0 Hz, 2H, S1CH2), 1.21 (t, 34H = 7.0 Hz, 9H, 10 CH3CH20), 2 , 15 (m, 2H, SiCH2CH2), 2.35 (s, 3H, plc-Me), 3.83 (c, 34, H = 7.0 Hz, 6H, CH3CH20), 3.95 (s, 3H , lmz-Me), 4.38 (t, 34, H = 8.0 Hz, 2H, CH2Imz), 6.90 and 6.96 (2 xd, 3.41.11 = 2.0 Hz, 2 x 1H, Imz-H4 and H5), 7.09 (d, 3JH, H = 5.9 Hz, 1H, m-pic), 8.83 (d, 34, H = 5.9 Hz, 1H, or- pic).  13C NMR {1H} (CDCI3, 75 MHz): 67.7 (SiCH2), 18.4 (CH3CH20), 21.1 (pic-Me), 23.1 (SiCH2CH2), 39.2 (lmz-Me) , 537 (CH2Imz), 58.6 (CH3CH20), 121.7 and 123.0 15 (Imz-C4 and C5), 125.3 (m-pic), 145.6 (Imz-C2), 149.4 (p-pic), 153.2 (o-pic).  IR (KBr): v 3050-3120 (m, Csp-H st), 1618 (m, C = C st), 1542 (s, C = N st), 1420-1470 (m, arC = C st), 1080 (w, Si-OC st), 957 (w, Si-OC st), 806 (m, Si-C st), 687 cm-1 (m, Si-0 st).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): ink 740.9418 [M + H.  20 (Et0) 3SiNN ,, I-Pd-I. ) 1 I (Yes) 1 Example 11.  Preparation of the palladium complex l (Si) 2.  Compound 1 (Si) 2 was prepared as described for complex 1 (S1) 1 of Example 25 10, starting from the imidazolium salt 2 (Si) 2 described in Example 5 (0.57 g, 1, 2 mmol), palladium chloride (0.21 g, 1.2 mmol), potassium carbonate (0.83 g, 6.0 mmol) and sodium iodide (1.26 g, 8.4 mmol), in 12 mL of 4-picoline, at 100 ° C and for 16 h.  Compound 1 (Si) 2 was obtained as an orange powdery solid (0.99 g, 98%).  Anal.  Calc.  for C27H4103N3I2SiPd (843.95): C, 38.43; H, 4.90; N, 4.98%.  Found: C, 38.22; 30 H, 4.78; N, 5.36%.  1H NMR (CDCI3, 300 MHz): 6 0.80 (t, JH, H = 8.2 Hz, 2H, S1CH2), 1.25 (t, 3JRH = 7.0 Hz, 9H, CH3CH20), 2, 25 (m, 2H, SiCH2CH2), 2.28 (s, 3H, pic-Me), 2.30 (s, 326H, Month-o-Me), 2.34 (s, 3H, Month-p-Me), 3.86 (c, 34, F, = 7.0 Hz, 6H, CH3CH20), 4.62 (t , 34, H = 7.0 Hz, 2H, CH2Imz), 6.87 and 7.24 (2 xd, 34, F, = 2.0 Hz, 2 x 1H, Imz-H4 and H5), 6.97 (s, 2H, m-Month), 6.98 (d, 34, H = 5.6 Hz, 2H, m-plc), 8.53 (d, 34, H = 5.6 Hz, 2H, or -pic).  13C NMR {1H} (CDCI3, 75 MHz): 6 7.7 (SiCH2), 18.4 (CH3CH20), 21.0 (Month-p-Me), 21.1 (pic-Me), 5 21, 7 (Month-o-Me), 23.3 (SiCH2CH2), 55.0 (CH2Imz), 58.6 (CH3CH20), 121.3 and 136.1 (lmz-y C5), 125.1 (m- plc), 129.4 (m-Month), 135.0 (ipso-Month), 139.0 (p-Month), 148.4 (o-Month), 149.1 (p-pic), 152, 9 (o-pic).  IR (KBr): v 3070-3160 (m, arC-H st), 1618 (m, arC = C st), 1531 (s, C = N st), 1400-1480 (m, arC = C st), 1076 (w, Si-OC st), 956 (w, Si-OC st), 806 (m, Si-C st), 692 cnri-1 (m, Si-0 st).  MS (ESIf / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 10 862.0312 [M + NH4], 845.0154 [M + H], 717.0939 [M-Ir.  I (Yes) 2 Example 12.  Preparation of the palladium complex l (Si) 3.  Compound 1 (Si) 3 was prepared similarly to that described for complex 1 (51) 1 of Example 10, starting from the imidazolium salt 2 (Si) 3 described in Example 6 (0.62 g, 1.2 mmol), palladium chloride (0.21 g, 1.2 mmol), potassium carbonate (0.83 g, 6.0 mmol) and sodium iodide (1.28 g, 8.4 mmol) , in 12 mL of 4-picoline, at 100 ° C and for 16 h.  Compound 1 (51) 3 was obtained as a powdery & Nick) orange powder (0.99 g, 98%).  Anal.  Calc.  for C30H4703N3I2S1Pd (843.95): C, 40.67; H, 5.35; N, 4.74%.  Found: C, 41.03; H, 5.75; N, 5.21%.  1H NMR (CDCI3, 300 MHz): 6 0.82 (d, 34, F, = 7.9 Hz, 2H, SiCH2), 0.99 (d, 3JH, H - = 6.9 Hz, 6H, CH (CH3) 2), 1.24 (t, 34, H = 6.9 Hz, 9H, CH3CH20), 1.38 (d, 34, H = 6.9 Hz, 6H, CH (CH3) 2), 2.23 (m, 2H, S1CH2CH2), 2.27 (s, 3H, plc-Me), 3.10 (h, 25 JH, H = 6.9 Hz, 6H, CH (CH3) 2), 3 , 85 (c, 3JH H = 6.9 Hz, 6H, CH3CH20), 4.68 (t, 34, H - = 7.9 Hz, 2H, CH2Imz), 6.98 (2 xt, 3H, 34, H = 6.6 Hz, 34, H = 2.0 Hz, Imz-H4 and o-pic, overlapping), 7.13 (d, 3JH, H = 2.0 Hz, 1H, Imz-H5), 7 , 28 ((1, 34, H = 7.9 Hz, 2H, m-Ph), 7.46 (t, 34, H = 7.9 Hz, 1H, p-Ph), 8.54 (d, 3JH, F, = 6.6 Hz, 2H, 0-plc).  13C NMR {1H} (CDCI3, 75 MHz): ô 7.7 (S1CH2), 18.4 (CH3CH20), 21.0 (plc-Me), 23.2 (S1CH2CH2), 23.9 (CH (CH3 ) 2), 26.5 30 (CH (CH3) 2), 28.8 (CH (CH3) 2), 55.4 (CH2Irnz), 58.6 (CH3CH20), 120.3 and 130.3 (Imz -C4 and C5), 124.2 (m-Ph), 125.1 (m-plc), 126.7 (p-Ph), 134.7 (ipso-Ph), 147.0 (o-Ph) , 149.1 (p-335 foot), 152.8 (o-pic).  ).  IR (KBr): v 3030-3133 (m, arC-H st), 1619 (m, arC = C st), 1503 (s, C = N st), 1400-1460 (m, arC = C st), 1077 (w, Si-OC st), 957 (w, Si-OC st), 804 (m, Si-C st), 692 cm-1 (m, Si-0 st).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): rn / z 904.0818 [M + Nftsr, 887.0560 [M + H].  / - = (Eto) 3si N and N-ip r2 Ph I-pd-I Example 13.  Prepared & Silver Complex 3 (Si) 1.  The imidazolium 2 (Si) 1 salt described in Example 4 (1.28 g, 3.5 mmol) and the silver oxide (0.40 g, 1.7 mmol) are weighed in a 50 mL ampoule. , and was empty for 10 min.  The solid was suspended in 10 mL of dichloromethane under argon and the mixture was allowed to stir at room temperature for 16 h in the absence of light.  After filtering to remove excess silver oxide, the resulting yellow solution was evaporated and the residue was washed with hexane (2 x 15 mL), yielding product 3 (Si) 1 as a yellow oily solid (1, 48 g, 95%), whose dissolving structure corresponds to a formulation [Ag (NHC) 2] [AgBr2] that gives the syn and anti rotamers (70:30) in equilibrium.  Anal.  Calc.  for C26H52N406Si2Ag2Br2 (948.43): C, 32.93; H, 5.53; N, 5.91%; Found: C, 32.93; H, 5.28; N, 5.93%.  1H NMR (CDCI3, 300 MHz): Anti isomer: 6 0.56 20 (t, 341, H = 7.7 Hz, 4H, SiCH2), 1.19 (t, 3JH, H = 6.9 Hz, 18H , CH3CH20), 1.88 (m, 4H, SiCH2CH2), 3.76 (s, 6H, lmz-Me), 3.78 (c, 34, H = 6.9 Hz, 12H, CH3CH20), 4, 08 (t, 34, H = 7.7 Hz, 4H, CH2Imz), 6.91 and 6.94 (d, 34, H = 1.5 Hz, 2H, Imz-H4 and Fr).  IsOmero syn: 6 0.55 (t, 34.11 = 7.7 Hz, 4H, SiCH2), 1.18 (t, 3.11-1.11 = 6.9 Hz, 18H, CH3CH20), 1, 88 (m, 4H, SiCH2CH2), 3.78 (c, 3. 401 = 6.9 Hz, 12H, CH3CH20), 3.79 (s, 6H, lmz-Me), 4.06 (t, 34, H = 25 7.7 Hz, 4H, CH2Imz), 6.93 and 6.98 (d, 3s / H, H = 1.5 Hz, 2H, Imz-H4 and Fr).  "G {1 H} NMR (CDCI3, 75 MHz): Anti isomer: 6 8.7 (SiCH2), 18.2 (CH3CH20), 25.6 (SiCH2CH2), 38.9 (lmz-Me), 54.1 (CH2Imz), 58.3 (CH3CH20), 121.2 and 122.1 (Imz-C4 and C5), 181.7 (Imz-C2).  IsOnnero syn: 67.3 (S1CH2), 18.2 (CH3CH20), 25.2 (S1CH2CH2), 38.7 (lmz-Me), 53.9 (CH2Imz), 58.5 (CH3CH20), 121.0 and 122.0 (Imz-C4 and C5), 181.2 (Imz-C2).  Diffusion coefficients DOSY-30 NMR (CDCI3, 25 ° C) in tomb at 6.0. 10-10 M2S-1 for the two rotameros.  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): nilz 681.2542 [Ag (NHC) 2], 287.1814 [NHC + H].  3. 4AgBr 3 (Yes) 1 Example 14.  Preparation of the silver complex 3 (51) 2.  Compound 3 (Si) 2 was prepared as described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (51) 2 described in Example 5 (2.69 g, 5, 7 mmol) and Silver Oxide (0.66 g, 2.8 mmol).  Complex 3 (Si) 2 was obtained as a yellow oily solid (3.07 g, 98%), whose structure in solution corresponds to a 10 [Ag (NHC) 2] [AgBr2] which gives rise to the rotameros syn and anti (70:30) in balance.  Anal.  Calc.  for C42H68N406Si2Ag2Br2-0.7CH2C12 (1207.69): C, 42.17; H, 5.75; N, 4.81%; Found: C, 41.83; H, 5.16; N, 5.27%.  1H NMR (CDCI3, 300 MHz): Anti and syn isomers: (50.57 (m, 8H, SiCH2), 1.21 (t, 3. 4th = 7.0 Hz, 36H, CH3CH20), 1.79 (m, 8H, SiCH2CH2), 1.93 (s, 24H, Month-o-Me), 2.29 (s, 12H, Month-p- Me), 3.79 (c, 34, H = 7.0 Hz, 15 24H, CH3CH20), 4.18 (m, 8H, CH2Imz), 6.89 and 7.18 (2 xd, 3JR, H = 1.5 Hz, 2 x 4H, Imz-H4 and H5), 6.91 (s, 8H, m-Month).  13C NMR {1H} (CDCI3, 75 MHz): Anti isomer: (58.5 (SiCH2), 17.7 (CH3CH20), 21.0 (Month-p-Me), 25.7 (SiCH2CH2), 29, 1 (Month-or-Me), 53.7 (CH2Imz), 58.1 (CH3CH20), 121.6 and 123.9 (Imz-C4 and C5), 129.4 (m-Month), 134.6 ( o-Month), 135.3 (ipso-Month), 139.1 (p-Month).  Isomer syn: 6 7.3 (SiCH2), 18.3 (CH3CH20), 21.0 (Month-p-Me), 25.3 20 (SiCH2CH2), 29.1 (Month-o-Me), 54, 0 (CH2Imz), 58.5 (CH3CH20), 120.9 and 122.5 (Imz-C4 and C5), 129.1 (m-Month), 134.7 (o-Month), 135.6 (ipso -Month), 139.3 (p-Month).  Diffusion coefficients DOSY-NMR (CDCI3, 25 ° C) around 5.8. 10. 10 M2S-1 for the two rotanneros.  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 889.3779 [Ag (NFIC) 2I.  25 1 == N N'mes AgBr 3 (Yes) 2 Example 15.  Preparation of the silver complex 3 (51) 3.  Compound 3 (Si) 3 was prepared as described for complex 3 (Si) 1 of Example 30 13, starting from the imidazolium salt 2 (Si) 3 described in Example 6 (2.50 g, 5, 2 mmol) and 35Silver oxide (0.60 g, 2.6 mmol).  Complex 3 (S1) 3 was obtained as a yellow oily solid (3.14 g, 98%), whose dissolving structure corresponds to a formulation [Ag (NHC) 2] [AgBr2] that results in the rotameros syn and anti (70:30) in balance.  Anal.  Calc.  for C48F180N406S12Ag2Br2 (1240.89): C, 46.46; H, 6.50; N, 4.51%; 5 Found: C, 46.84; H, 6.88; N, 5.01%.  1H NMR (CDCI3, 300 MHz): Anti and syn isomers: (50.67 (m, 8H, S1CH2), 1.15 (d, 3.4th = 6.6 Hz, 24H, CH (CH3) 2), 1.20 (d, 34, Ei = 6.6 Hz, 24H, CH (CH3) 2), 1.21 (t, 34, H = 7.0 Hz, 36H, CH3CH20), 2.03 (m, 8H, SiCH2CH2), 2.36 (Sep. , 3JKH = 6.6 Hz, 8H, CH (CH3) 2), 3.85 (c, 34.11 = 7.0 Hz, 24H, CH3CH20), 4.33 (m, 8H, CH2Imz), 7, 00 and 7.20 (2 xd, 3. 4tH = 1.7 Hz. 2 x 4H, Imz-H4 and H5), 7.22 (d, 341, H = 7.7 Hz, 10 8H, m-Ph), 7.47 (t, 3JH, H = 7.7 Hz, 4H , p-Ph).  13C NMR {1H} (CDCI3, 75 MHz): Anti isomer: (57.5 (SiCH2), 18.3 (CH3CH20), 24.3 (CH (CH3) 2), 25.4 (SiCH2CH2), 28, 1 (CH (CH3) 2), 54.1 (CH2Imz), 58.6 (CH3CH20), 121.5 and 123.7 (Imz-C4 and C5), 124.2 (p-Ph), 129.7 (m-Ph), 145.6 (0-Ph), 145.9 (ipso-Ph).  IsOmero syn: (5 7.3 (SiCH2), 18.3 (CH3CH20), 24.5 (CH (CH3) 2), 25.2 (SiCH2CH2), 28.3 (CH (CH3) 2), 53, 7 (CH2Imz), 58.5 (CH3CH20), 121.5 and 15 123.7 (Imz-C4 and C5), 125.7 (p-Ph), 130.5 (m-Ph), 145.6 ( 0-Ph), 145.9 (ipso-Ph).  Diffusion coefficients DOSY-NMR (CDCI3, 25 ° C) in volume at 5.7. 10-10 M2S. 1 for both rotameros.  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 973.4667 [Ag (NHC) 2] +.  20 / = AgBr 3 (Yes) 3 Example 16.  Preparation of the silver complex 3 (A) 1.  Compound 3 (A) 1 is prepared) in a manner similar to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 1 described in Example 7 (0.80 g , 3.7 mmol) and silver oxide (0.43 g, 1.9 mmol).  Complex 3 (A) 1 was obtained as a yellow oily solid (1.03 g, 88%).  Anal.  Calc.  for C6FI11N3AgBr. 0.1C6H14 (321.56): C, 24.65; H, 3.89; N, 13.07%; Found: C, 24.95; H, 4.09; N, 13.25%.  1H NMR (CDCI3, 300 MHz): 63.09 (t, 34, H = 5.5 Hz, 2H, NH2CH2), 3.83 (s, 3H, Imz-Me), 4.14 (t, 34tH = 5.5 30 Hz, 2H, CH2Imz), 6.96 and 7.05 (2 xd, 3JH, H = 1.8 Hz, 2 x 1H, Imz-H4 and H5).  13C NMR {1H} (CDCI3, 75 MHz): 638.8 (Imz-Me), 42.9 (NH2CH2), 54.7 (CH2Imz), 121.6 and 122.1 (Imz-C4 and C5), 180.8 (Imz-C2).  MS (ESI + / TOF, CH2C1) / Me0H / 5mM NH4HCOO): rniz 287.1763 [M-Br + 3H2O].  36/ = H2N N and AgBr 3 (A) 1 Example 17.  Preparation of the silver complex 3 (A) 2.  Compound 3 (A) 2 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 2 described in Example 8 (3.20 g, 10.0 rnmol) and silver oxide (1.18 g, 5.1 mmol).  Complex 3 (A) 2 was obtained as a yellow oily solid (3.60 g, 86%).  Anal.  Calc.  for C14H19N3AgBr. 0.15 (C6F114) 10 (430.02): C, 41.61; H, 4.95; N, 9.77%; Found: C, 42.07; H, 4.91; N, 10.29%.  1H NMR (CDCI3, 300 MHz): 6 1.93 (s, 6H, Month-o-Me), 2.31 (s, 3H, Month-p-Me), 3.15 (t, 34H = 5, 6 Hz, 2H, NH2CH2), 4.25 (1, 34, H = 5.6 Hz, 2H, CH2Imz), 6.91 and 7.28 (2 xd, 34, H = 1.7 Hz, 2 x 1H, Imz-H4 and H5), 6.92 (s, 2H, m-Month).  13C NMR {1H} (CDCI3, 75 MHz): 6 17.7 (Month-p-Me), 21.1 (Month-o-Me), 43.1 (CH2Imz), 55.0 (NH2CH2), 121 , 4 and 122.6 (Imz-C4 and C5), 129.4 15 (m-Month), 135.3 (ipso-Month), 134.6 (o-Month), 139.6 (p-Month) , 180.2 (Imz-C2).  MS (ES1 + / TOF CH2C12 / Me0H / 5mM NH4HCOO): m / z 230. 1656 [M - AgBr + H].  H2N "---- 1yN-Month AgBr 3 (A) 2 20 Example 18.  Preparation of the silver complex 3 (A) 3.  Compound 3 (A) 3 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 3 described in Example 9 (3.60 g, 10 , 3 mmol) and silver oxide (1.18 g, 5.1 mmol).  Complex 3 (A) 3 was obtained as a yellow oily solid (4.30 g, 90%).  Anal.  Calc.  for C17H25N3AgBr. 0.25 (C6I-I14) (480.72): C, 46.22; H, 5.98; N, 8.74%; Found: C, 46.75; H, 5.72; N, 8.53%.  1 H NMR (CDCI3, 300 MHz): 61.11 (d, 3.41, H = 6.9 Hz, 12H, CH (CH3) 2), 1.18 (d, JH, H = 6.9 Hz, 12H , CH (CH3) 2), 2.32 (Sep. , 3. 4th = 6.9 Hz, 2H, (C1-13) 2CH), 3.17 (t, 34, H = 5.8 Hz, 2H, NH2CH2), 4.26 (t, 3JKH = 5.8 Hz, 2H, CH2Imz), 6.98 and 7.31 (2 xd, 3JH, H = 1.5 Hz, 2 x 1H, Imz-H4 and 30 H5), 7.23 (d, 3. 4tH = 7.7 Hz, 2H, m-Ph), 7.45 (t, 34, H = 7.7 Hz, 1H, p-Ph).  13 C NMR {1H} 375 (CDCI3, 75 MHz): 6 24.3 (CH (CH3) 2), 24.6 (CH (CH3) 2), 28.3 (CH (CH3) 2), 43.2 (NH2CH2), 55 , 0 (CH2Imz), 121.2 and 123.9 (Irriz-C4 and C5), 124.3 (m-Ph), 130.5 (ipso-Ph), 134.6 (o-Ph), 145, 6 (p-Ph), 182.8 (Imz-C2).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 272.2139 [M-AgBr + H].  Fi2NNy N'iPr2Ph AgBr 3 (A) 3 Example 19.  Preparation of palladium complex 11 (S1) 1.  In a 50 mL ampoule, the silver carbine 3 (Si) 1 described in Example 13 (0.39 g, 0.87 mmol) and PdBr2 (COD) (0.16 g, 0.43 mmol; COD = 1,5-cyclooctadiene).  After the solids were subjected to vacuum for 5 min, the solid was dissolved under argon in 10 mL of dichloromethane and the resulting orange solution was allowed to stir at room temperature for 1 h.  The mixture was filtered to separate the silver halide that formed as a secondary product, the resulting yellow solution was evaporated and washed with hexane (2 x 15 mL), yielding product II (Si) 1 as a powdery solid. Arnarillo color (0.65 g, 89%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotamers (50:50) in equilibrium.  Anal.  Calc.  for C26H52N406Si2PdBr2 (839.11): C, 37.22; H 3.25; N 6.68%; Found: C, 36.97; H, 6.07; 20 N, 6.79%.  1H NMR (CDCI3, 300 MHz): IsOrnero anti: 6 0.72 (m, 4H, SiCH2), 1.20 (t, 3J1-1, H = 6.9 Hz, 18H, CH3CH20), 2.20 ( m, 4H, SiCH2CH2), 3.81 (c, 3JH, H = 6.9 Hz, 12H, CH3CH20), 4.06 (s, 6H, Imz-Me), 4.44 (m, 4H, CH2Imz) , 6.79 and 6.88 (2 xd, 3. 1H, H = 1.7 Hz, 2 x 2H, Imz-H4 and H5).  IsOmero syn: 60.72 (m, 4H, SiCH2), 1.20 (t, 3. . / H, H = 6.9 Hz, 18H, CH3CH20), 2.20 (m, 4H, SiCH2CH2), 3.81 (c, 34tH = 6.9 Hz, 12H, CH3CH20), 4.03 (s, 6H, lmz-Me), 4.44 (m, 4H, CH2Imz), 6.79 and 6.86 (2 xd, 34. 1, H = 1.7 Hz, 2 x 2H, Imz-H4 and H5).  13C NMR (1H) (CDCI3, 75 MHz): Isomer ° anti: 6 7.7 (SiCH2), 18.3 (CH3CH20), 24.4 (SiCH2CF12), 37.9 (lmz-Me), 53.1 (CH2Imz), 58.6 (CH3CFI20), 121.1 and 121.8 (Imz-C4 and C5), 169.2 (Imz-C4).  IsOmero syn: 6 7.5 (SiCH2), 18.3 (CH3CH20), 24.3 (SiCH2CH2), 37.9 (Imz-Me), 52.8 (CH2Imz), 58.5 (CH3CH20), 121, 0 and 121.7 (Imz-C4 and C5), 169.2 (Imz-C2).  IR (KBr): v 3080-3030 (m, arC-H st), 1525 (s, C = N st), 1380-1480 (m, arC = C st), 1080 (w, Si-OC st) , 960 (w, Si-OC st), 720-790 (m, Si-C st), 690 cm-1 (m, Si-0 st).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 856.1157 [M + NH41 +, 759.1635 [M-Br].  38Br-Pd-Br, INNSi (OEt) 3 ==. 1 II (Yes) 1 Example 20.  Preparation of palladium complex 11 (S1) 2.  5 Compound II (Si) 2 was prepared in the same manner as compound II (Si) 1 of Example 19, starting from the silver carbine 3 (Si) 2 described in Example 14 (0.45 g, 0.81 mmol ) and PdBr2 (COD) (0.15 g, 0.41 mmol).  Complex 11 (S1) 2 was obtained as a yellow powdery solid (0.83 g 97%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotameros (56:44) in Balance.  10 Anal.  Cale.  C42F168N406Si2PdBr2 (1047.41): C, 48.16; H, 6.54; N, 5.35%; Found: C, 48.41; H, 6.44; N, 5.41%.  1H NMR (CDCI3, 300 MHz): Anti-Isomer: 0.47 (m, 4H, SiCH2), 1.20 (m, 18H, CH3CH20), 1.89 (m, 4H, SiCH2CH2), 2.22 (s , 12H, Month-o-Me), 2.33 (s, 6H, Month-p-Me), 3.83 (m, 12H, CH3CH20), 4.17 (m, 4H, CH2Imz), 6.70 and 6.98 (2 xd, 34, H = 1.5 Hz, 2 x 2H, Imz-H4 and H5), 6.94 (s, 4H, m-Month).  Isomer syn: 6 0.73 (m, 4H, SiCH2), 1.23 15 (m, 18H, CH3CH20), 1.89 (m, 4H, SiCH2CH2), 1.91 (s, 12H, Month-o- Me), 2.43 (s, 6H, Month-p-Me), 3.81 (m, 12H, CH3CH20), 4.61 (m, 4H, CH2Imz), 6.63 and 6.93 (2 xd , 34, H = 1.5 Hz, 2 x 2H, Imz-H4 and H5), 6.81 (s, 4H, m-Month).  13C NMR {1H} (CDCI3, 75 MHz): Anti isomer Number: 6 7.1 (SiCH2), 18.4 (CH3CH20), 19.4 (Month-p-Me), 23.9 (SiCH2CH2), 29, 7 (Month-or-Me), 53.1 (CH2Imz), 58.4 (CH3CH20), 120.8 and 122.7 (Imz-C4 and C5), 128.8 (m-Month), 136.0 (ipso-20 Month), 136.6 (o-Month), 138.2 (p-Me), 169.7 (Imz-C2).  Isonnero syn: 6 7.5 (SiCH2), 19.8 (CH3CH20), 21.0 (Month-p-Me), 24.3 (S1CH2CH2), 29.3 (Month-o-Me), 53.7 (CH2Imz), 58.4 (CH3CH20), 121.1 and 122.7 (Imz-C4 and C5), 128.7 (m-Month), 135.5 (ipso-Month), 135.9 (o- Month), 137.4 (p-Month), 169.6 (Imz-C2).  IR (KBr): v 3080-3170 (m, arC-H st), 1620 (m, arC = C st), 1590 (s, C = N st), 1380-1450 (m, arC = C st), 1072 (w, Si-OC st), 943 (w, Si-OC st), 722-25800 (m, Si-C st), 703 cm-1 (m, Si-0 st).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4FICOO): m / z 1064.2414 [M + NH4].  39f = N N yes (OEt) 3 II (Si) 2 Example 21.  Preparation of the paladioll complex (S1) 3.  5 Compound II (Si) 3 was prepared as described for compound II (Si) 1 of Example 19, starting from silver carbene 3 (Si) 3 described in Example 15 (0.44 g, 0.70 mmol) and PdBr2 (COD) (0.13 g, 0.35 mmol).  Complex II (Si) 3 was obtained as a yellow powdery solid ° (0.75 g, 95%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotamers (60:40 ) in equilibrium.  10 Anal.  Calc.  C48F180N406S12PdBr2 (1131.57): C, 50.95; H, 7.13; N, 4.95%; Found: C, 50.86; H 6.63; N 5.07%.  1H NMR (DMSO-d6, 300 MHz): Anti isomer: or 0.49 (m, 4H, SiCH2), 1.13 (m, 42H, CH (CH3) 2, CH3CH20), 1.89 (m, 4H , S1CH2CH2), 2.45 (m, 4H, CH (CH3) 2), 3.72 (m, 12H, CH3CH20), 4.07 (m, 4H, CH2Imz), 7.15-7.80 (m , 10H, and H5, p-Ph, m-Ph).  IsOmero syn: 6 0.58 (m, 4H, SiCH2), 1.13 (m, 42H, CH (CH3) 2, CH3CH20), 15 1.89 (m, 4H, SiCH2CH2), 2.45 (m, 4H, CH (CH3) 2), 3.72 (m, 12H, CH3CH20), 4.20 (m, 4H, CH2Imz), 7.15-7.80 (m, 10H, and H5, p-Ph, m-Ph).  13C NMR (1H) (DMSO-d6, 75 MHz): 6 8.7 (SiCH2), 14.6 (CH3CH20), 23.1 (SiCH2CH2), 23.6 (CH (C1-13) 2), 27 , 3 (CH (CH3) 2), 52.6 (CH2Imz), 57.4 (CH3CH20), 121.1 and 122.2 (Imz-C4 and C5), 123.4 (p-Ph), 129, 6 (m-Ph), 134.1 (ipso-Ph), 144.4 (o-Ph).  IR (KBr): v 3030-3120 (m, arC-H st), 1625 (m, arC = C st), 20 1512 (s, C = N st), 1330-1500 (m, arC = C st) , 1123 (w, Si-OC st), 946 (w, Si-OC st), 700-800 (m, Si-C st), 685 cm-1 (m, Si-0 st).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): mtz 899.3888 [M - 4Et0H - Br + Me0H], 856.1127 [M - 5Et0H - Br + NH401-11 +, 776.1865 [M - 6Et0H - Brr.  25 (Et0) 3S1NyN'1Pr2Ph Br-Pd-Br PhiPr2-1, (INNi (OEt) II (Si) 3 Example 22.  Preparation of palladium II complex (A) 1.  40Compound II (A) 1 be prepared) as described for compound II (Si) 1 of Example 19, starting from the silver carbine 3 (A) 1 described in Example 16 (1.00 g, 3.2 mmol) and PdBr2 (COD) (0.60 g, 1.6 mmol).  Complex II (A) 1 was obtained as an oily yellow solid ° 5 (0.70 g, 85%), whose characterization by NMR required its transformation into the ammonium salt, [II (A) 1] 2+ , for treatment with an excess of NH4CI and whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotamers (30:70) in equilibrium.  Anal.  Cale.  C12H22N6PdBr2 (516.57): C, 27.90; H, 4.29; N, 16.27%; Found: C, 28.10; H, 4.76; N, 16.05%.  1H NMR (DMSO-d6, 300 MHz, [II (A) 1] 2+): 10 Anti isomer: 6 2.88 (t, 34th = 5.6 Hz, 4H, CH2Imz), 3.83 (s, 6H, Imz-Me), 4.08 (t, 3JH, H = "5.6 Hz, 4H, NH2CH2), 7.67 and 7.70 (2 xs, 2 x 2H, Imz-H4 and H5).  Isomer ° syn: 6 2.88 (t, = 5.6 Hz, 4H, CH2Imz), 3.74 (s, 6H, Imz-Me), 4.24 (t, 34, H = 5.6 Hz, 4H, NH2CH2), 7.40 and 7.43 (2 xs, 2 x 2H, Imz-H4 and H5).  13C NMR {1H} (DMSO-d6, 75 MHz, [II (A) 1] 2+): Anti isomer: 6 37.6 (Imz-Me), 40.8 (CH2Imz), 51.5 (NH2CH2) , 122.0 and 122.8 (Imz-C4 and 15 C6), 177.8 (Imz-C2).  gHMBC- {1H, 16N} (CDCI3, 293K): 6 -190 (Num), -198 (km), -345 (NH2).  MS (ES1 ÷ / TOF, CH2C12 / Me0H / 5 mM NH4HCOO): at & 453.1629 [M - HBr NH4l ÷, 436.1562 [M - Br], 355.0865 [M -HBr - Br].  20 ir = H2 NyN 1 1- 'Br-Pd-Br II (A) 1 Example 23.  Preparation of palladium complex II (A) 2.  Compound II (A) 2 was prepared as a coma described for compound II (Si) 1 of Example 19, starting from plate 3 (A) 2 carbine described in Example 17 (0.50 g, 1.2 25 mmol) and PdBr2 (COD) (0.22 g, 0.60 mmol).  Corn complex II (A) 2 was obtained as an oily yellow solid (0.38 g, 88%), whose characterization for NMR required its transformation into the ammonium salt, [II (A) 212, for treatment with an excess of NH4Cly whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotameros (20:80) in equilibrium.  Anal.  Cale.  C28H38N6PdBr2 (724.87): C, 46.39; H, 5.28; N, 11.59%; 30 Found: C, 46.44; H, 5.78; N, 11.59%.  1H NMR (DMSO-d6, 300 MHz, [II (A) 2] 2+): Isomer ° anti: 6 1.85 (s, 12H, Month-o-Me), 2.32 (s, 6H, Month -p-Me), 2.93 (t, 34, H = 5.8 Hz, 414H, CH2Imz), 4.12 (t, 341.11 = 5.8 Hz, 4H, NH2CH2), 7.02 (s, 4H, m-Month), 7.44 and 7.67 (2 xd, 3 . 41, H = 1.8 Hz, 2 x 2H, Imz-H4 and H5).  IsOmero syn: (51.91 (s, 12H, Month-o-Me), 2.36 (s, 6H, Month-p-Me), 2.96 (t, 3. 41, H = 5.8 Hz, 4H, CH2Imz), 4.19 (t, 3JitH = 5.8 Hz, 4H, NH2CH2), 6.92 (s, 4H, m-Month), 7.36 and 7 , 62 (2 xd, 3JH, H = 1.7 Hz, 2 x 2H, Imz-H4 and H5).  13C NMR {1H} 5 (DMSO-d6, 75 MHz, [II (A) 2] 2+): Anti isomer: (516.7 (Month-p-Me), 20.1 (Month-or-Me) , 43.4 (CH2Imz), 53.6 (NH2CH2), 121.9 and 122.5 (Imz-C4y C5), 128.4 (m-Month), 128.7 (ipso-Month), 134.0 (o-Month), 137.9 (p-Month), 171.5 (Imz-C2).  gHMBC- {1H, 15N} (CDCI3, 293K): (5-191 (Nimz), -192 (Nirriz), -368 (NH2).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): m / z 644.9697 [M-Br], 563.2124 [M-Br-HBr] +.  10 / = NyN. month H2N Br-Pd-Br Month -NH2 N N - _ = / II (A) 2 Example 24.  Preparation of the palladium II complex (A) 3.  Compound II (A) 3 was prepared as described for compound II (Si) 1 of Example 19, starting from the silver carbine 3 (A) 3 described in Example 18 (0.50 g, 0.85 nmol) and PdBr2 (COD) (0.16 g, 0.42 mmol).  Complex II (A) 3 was obtained as an oily yellow solid (0.58 g, 84%), whose NMR characterization required its transformation into the ammonium salt, [II (A) 3] 2+, by treatment with an excess of NRICI and whose structure 20 in solution corresponds to the presence of the trans-syn and trans-anti rotamers (25:75) in equilibrium.  Anal.  Calc.  C34HSON6PdBr2 (809.03): C, 50.48; H, 6.23; N, 10.39%; Found: C, 50.07; H, 5.98; N, 10.13%.  1H NMR (DMSO-d6, 300 MHz, [II (A) 3] 2+): Anti isomer: 61.07 (d, 3.4tH = 6.9 Hz, 24H, CH (CH3) 2), 2, 26 (Sep. , 3JKH = 6.9 Hz, 4H, CH (CH3) 2), 2.89 (m, 4H, CH2Imz), 4.08 (m, 4H, NH2CH2), 7.32 (d, 3JKH = 7.9 Hz, 4H, m-25 Ph), 7.49 (t, 3JH, H = 7.9 Hz, 2H, p-Ph), 7.61 and 7.71 (2 xd, 3JH, H = 1.6 Hz, 2 x 2H, Innz-H4 and H5).  IsOmero syn: 61.12 (d, 34H = 6.9 Hz, 24H, CH (CH3) 2), 2.26 (Sep. , 3JH, H = 6.9 Hz, 4H, CH (CH3) 2), 2.99 (m, 4H, CH2Imz), 4.22 (m, 4H, NH2CH2), 7.32 (d, 3. 404 = 7.7 Hz, 4H, m-Ph), 7.45 (t, 3JH, H = 7.7 Hz, 2H, p-Ph), 7.59 and 7.67 (2 xd, 34H = 1 , 5 Hz, 2 x 2H, Imz-H4 and H5).  13C {1H} NMR (DMSO-d6, 75 MHz, [II (A) 3] 2+): Anti isomer: 23.3 (CH (CH3) 2), 23.6 30 CH (CH3) 2), 27 , 2 (CH (CH3) 2), 42.5 (CH2Innz), 53.5 (NH2CH2), 121.9 and 123.9 (Imz-C4 and C5), 123.4 (m-Ph), 129, 5 (ipso-Ph), 134.5 (o-Ph), 144.9 (p-Ph), 181.3 (Imz-C2).  gHMBC- {1H, 4215N} (CDCI3, 293K): 6-187 (Nim,), --205 (Nmz), -377 (NH2).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NR4HCOO): m / z 837.3255 [M-Br + HCOOH + HCOONH4r, 755.4001 [M-2HBr + 2HCOOH + NH4].  H2N '. --NyN'1Pr2Ph Br-Pd-Br II (A) 3 Example 25.  Preparation of the imidazolium salt 4. Four.  In a 25 mL ampoule, the starting bis (imidazolyl) methane (0.26 g, 1.7 mmol) 10 and the N- (2-bromoethyl) phthalimide (1.11 g, 4.4 mmol) were placed.  After the solids were subjected to vacuum for 5 min, they were dissolved in 5 mL of dry CH3CN and the resulting solution was heated at 120 ° C for 48 h.  After filtering and drying the solid °, salt 4 was obtained. 4 as a white powdery solid ° (1.05 g, 91%).  Anal.  Calc.  for C27F124N604Br2. 2H20 (692.36): C, 46.84; H, 4.08; N, 12.14%; Found: C, 47.03; H, 4.01; N, 12.03%.  1H NMR (DMSO-d6, 300 MHz): 6 3.99 (t, 34, H = 4.6 Hz, 4H, CH2ftal), 4.53 (t, 3.44, H = 4.6 Hz, 4H , CH2Imz), 6.71 (s, 2H, CH2), 7.82 (s, 8H, o-ftal, m-ftal), 7.92 and 8.02 (2 xs, 2 x 2H, Imz-H4 and H5), 9.56 (s, 2H, Imz-H2).  13C NMR {1H} (DMSO-d6, 75 MHz): 6 37.4 (CH2ftal), 47.9 (CH2Imz), 57.8 (CH2), 121.5 and 123.4 (Imz-C4 and C5) , 122.7 (o-ftal), 131.0 (ipso-ftal), 134.1 (m-ftal), 137.6 (Imz-C2), 167.2 (C = 0).  MS (ESI + / TOF, 20 CH2C12 / Me0H / NH4HCOO 5 nnM): m / z 495.1763 [M-HBr-Br].  25 N1 1.1: 1 1 r) Br-Br 4. 4 Example 26.  Preparation of palladium chelate complex 5. Four.  43The bisimidazolium 4 salt is weighed in a 15 mL ampoule with screw cap. 4 described in Example 25 (0.50 g, 0.76 mnnol) and dissolved in 1 mL of DMSO, an equivalent of palladium acetate (0.17 g, 0.76 mmol) was added on that solution.  The resulting suspension was heated at 50 ° C with stirring for 2 h.  After these 2 hours, the temperature was gradually increased to 110 ° C over 3 hours.  The resulting reddish solution was passed () through a celite column about 2.0 cm high and 1.5 cm in diameter.  After evaporating the DMSO and drying the solid, palladium chelate carbonate 5 was obtained. 4 conno a solid ° of gray color (0.49 g, 85%).  Anal.  Calc.  for C27H22N604PdBr2. H20 (778.74): C, 41.64; H, 3.11; N, 10.79%; Found: C, 41.48; H, 10 3.23; N, 10.95%.  1H NMR (DMSO-d6, 300 MHz): 3.80-4.10 (2 xm, 2 x 2H, CH2ftal), 4.11 and 5.15 (2 xm, 2 x 2H, CH2Imz), 6.25 (m, 2H, CH2), 7.33 and 7.52 (2 xs, 2 x 1H, Imz-H4 and H5), 7.60 (s, 8H, o-ftal and m-ftal).  13C NMR {1H} (DMSO-d6, 75 MHz): 6 37.5 (CH2ftal), 48.5 (CH2Imz), 62.1 (CH2), 120.8 and 121.3 (Imz-C4 and C5) , 122.3 (o-ftal), 130.7 (ipso-ftal), 133.6 (m-ftal), 159.6 (Imz-C2), 166.7 (C = 0).  MS (ESI + / TOF, CH2C12 / 5 mM MeOHNH4HCOO): 15 m / z 761,039 [M + H], 697,126 [M - HBr + NH4] +, 617,086 [M - 2HBr +) -N Br L-1 0 0 5. 4 Example 27.  Preparation of palladium chelate complex III (A) 4.  20 The palladium complex 5 is weighed in a 25 mL ampoule. 4 described in Example 26 (1.00 g, 1.3 mmol) and dissolved in 2 mL of dry CH3CN.  On the suspension formed, 40 equivalents of hydrazine (2.50 mL, 52.0 mmol) were added, giving a clear solution.  After one hour of reaction at room temperature, the phthanylhydrazine 25 formed was filtered, the solvent was evaporated and washed) with hot THF using a soxhlet equipment, yielding product III (A) 4 curio a solid ° beige (0.50 g , 82%).  Anal.  Lime.  for C11H201 160PdBr2. H20 (518.54): C, 2548; H, 3.89; N, 16.21%; Found C, 25.46; H, 4.02; N, 16.23%.  1H NMR (DMSO-d6, 300 MHz): 53.03 (wide s, 4H, CH2Imz), 4.23 (wide s, 4H, NH2CH2), 4.70 (wide s, 4H, NH2), 6.34 (s, 2H, CH2), 7.62 and 7.69 (2 xs, 2 x 30 1H, Imz-H4 and Fr).  13C NMR {1H} (DMSO-d6, 75 MHz): 6 40.3 (CH2Imz), 49.3 (NH2CF12), 4461.3 (CH2), 120.6 and 122.7 (Imz-C4 and C5), 152.0 (Imz-C2).  gHMBC- {1H, 15N} (DMSO-d6, 293K): 5197 (Nim,), —203 (Nim,), —381 (NH2).  IR (KBr): v 3393 (NH2 st), 3030-3100 (m, arC-H st), 1590-1610 (m, arC = C st), 1530 (s, C = N st), 1395-1480 cm -1 (m, arC = C st).  MS (ESI + / TOF, CH2C12 / Me0H / 5mM NH4HCOO): miz 420.9814 [M-Br], 365.1714 [M-2HBr 5 + Na], 339.0556 [M-HBr-Br].  eN) —N Pd r Br / 'Br -1 H2N NH2 Example 28.  Preparation of PMC (S1) 11.  10 III (A) 4 In a 25 mL Eppendorf vial 15 mg of silicon-coated PMs (Silica-Adembeads 300 nm from Ademtech) were added: nude of maghemite (y-Fe203); metal oxide content> 70%, magnetization of saturation: 40 emu / g; grain density: 1.8-2 g / cm3; specific surface area 10 m2 / g), 1 mL of Tx (Tx = aqueous solution of TritonTm X405 at 15 0.21% v), 1 mL of ethanol and 175 pL of a 30% aqueous solution of ammonia, to then sonicate the sample using a 200 W model 200200 UPS Hielscher instrument, for 5 min and half its maximum power.  In another vial the complex l (Si) 1 described in Example 10 (93.75 pmol) was weighed and dissolved in 4.5 mL of ethanol.  Under mechanical agitation (using a Bioshake iQ agitator / heater from Qlnstruments) over 20 the suspension of PMs was added dropwise drop the solution of the complex for 2.5 h, at 25 ° C and 750 rpm and sonicating every 15 min to favor the dispersion of the particles.  It was then heated to 40 ° C and allowed to stir 1 h more at 750 rpm.  With the help of an external magnet, the solution was decanted and the particles were washed with ethanol, with 5 mL fractions until the washings were colorless, then washed with 25 Pluronic0 F127 (0.30% v) (3 x 5 mL ) and finally with Tx (3 x 5 mL).  PMC (S1) 11 was obtained as a brown powdery solid, which was stored at 5 ° C dispersed in 5 mL of 0.21% Tx.  ICP-MS: 0.28% w Pd.  IR ATR: v 1620 (m, arC = C st), 1502 (s, C = N st), 1380-1480 (m, arC = C st), 800 cm-1 (m, Si-C st).  TEM: magnetic stress particles of size between 280-340 nm with an average thickness 30 of the silicon coating of 1.5 nm for the silica layer.  Four. FivePMC (Yes) 11 Example 29.  PMC Preparation (SI) 12.  -N 5 The PMC (Si) I2 were prepared as described for PMC (Si) 11 in Example 28, but using the complex l (S1) 2 described in Example 11.  They were obtained as a brown, powdery solid, which is preserved at 5 ° C dispersed in 5 mL of 0.21% Tx.  ICP-MS: 0.77% w Pd.  IR ATR: v 1615 (m, arC = C st), 1501 (s, C = N st), 1380-1480 (m, arC = C st), 780 cm-1 (m, Si-C st).  TEM: spherical magnetic particles of tamatium 10 comprised between 265-345 nm with an average thickness of the silica coating of 2.0 nm for the silica layer.  PMC (Yes) 12 15 Example 30.  PMC Preparation (SI) 13.  PMC (S1) 13 were prepared as described for PMC (Si) 11 in Example 28, but using the complex l (Si) 3 described in Example 12.  They were obtained as a powdery solid marrem color, which was stored at 5 ° C dispersed in 5 mL of 0.21% Tx.  20 ICP-MS: 0.66% w Pd.  IR ATR: v 1560-1640 (m, arC = C st), 1330-1480 (m, arC = C st), 770 cm- (m, Si-C st).  TEM: spherical magnetic particles of tamatium between 280-350 nm.  46—0, HO; Yes N N ,.  —0 and Pr2Ph 1 — Pd — I PMC (Yes) 13 Example 31.  Preparation of PMC (S1) 111.  5 The PMCs (Si) 111 were prepared as described for PMCs (Si) 11 in Example 28, but using the complex II (Si) 1 described in Example 19.  A powdery brown solid, which is preserved) at 5 ° C dispersed in 5 mL of 0.21% Tx was obtained.  ICP-MS: 0.24% w Pd.  IR ATR: v3080-3150 (m, arC-H st), 1380-1530 (m, C = N st, arC = C st).  TEM: spherical magnetic particles of size between 260-330 10 nm.  LOSI 0 —0 'and Br — Pd-Br —0, -If 1-0 ‘= _ / PMC (S1) 111 Example 32.  Preparation of PMC (S1) 112.  The PMC (S1) 112 were prepared as described in PMC (S1) 11 in Example 28, but using the complex II (S1) 2 described in Example 20.  They were obtained as a brown powdery solid, which was stored at 5 ° C dispersed in 5 mL of 0.21% Tx.  ICP-MS: 0.51% w Pd.  IR ATR: v 3060-3200 (m, arC-H st), 1620-1650 (s, arC = C 20 st), 1350-1520 (m, C = N st, arC = C st).  TEM: spherical magnetic particles of tamatium between 290-350 nm.  47a) / - = C: I; Yes, NyN, month —0 0. 0 Br — Pd-Br = in F ° C) 3Si -'----. 'N N' PMC (Yes) 112 Example 33.  Preparation of PMC (S1) 113.  Month —N 5 The PMC (S1) 113 were prepared as described for PMC (Si) 11 in Example 28, but using the complex II (51) 3 described in Example 21.  They were obtained as a powdery brown solid, which was stored at 5 ° C dispersed in 5 mL of 0.21% Tx.  ICP-MS: 0.43% w Pd.  IR ATR: v 3050-3180 (m, arC-H st), 1620-1650 (s, arC = C st), 1380-1520 (m, C = N st, arC = C st).  TEM: spherical magnetic particles of tamarum 10 comprised between 280-360 nm.  0, / = N. .  0 'and' Pr2Ph Br — Pd-Br 0, iPr2Ph 1: 2 (PMC (Si) 113 Example 34.  Prepared & from PMC (A) I11.  15 In a 5 mL vial, 15 mg of PMs coated with crosslinked polystyrene functionalized with carboxylic acid groups (Carboxyl-Adembeads 200 nm from Ademtech: nude of maghemite (y-Fe203), metal oxide content> 70%, were weighed. Saturation nnagnetization: 40 emu / g; 300 mmol COOH / g of MNPs, density of COOH groups on 20 surface: 20 pmol / m2, grain density: 1.8-2 g / cm3; specific surface 15 m2 / g) which were suspended in 1.5 mL of Tx / Me0H (2: 1; Tx = 0.21% TritOnTm X405 aqueous solution) and sonicated with a 200 W UPS200S Hielscher model for 5 min. its maximum power.  On the other hand, a DMF solution of complex 11 (A) 1 described in Example 22 (45 pmol) was prepared.  25 250 pL of both mixtures were placed in six Eppendorf 1.5 mL vials used, so that 48each contained 0.75 pmol of COOH groups and 15.0 pmol of NH groups, and on each one 200 pL of a solution of carbodiimide CHMC (N-cyclohexyl-N '- (24N-methylmorpholinolethyl) carbodiimide) was added. in Tx ([CHMC] = 0.03 m. Each Eppendorf vial was completed with 350 pL of Tx / Me0H (2: 1) to a final volume of 1 mL in 5 each vial.  Once the six samples were prepared, they were placed under mechanical agitation (using a Stuart rotator SB2 carousel stirrer) at 20 rpm for 16 h at room temperature.  After the solutions were decanted with the help of a magnet, the Table 3 samples were washed successively with an aqueous solution of 10 mm NaOH (2 x 1 mL), with Tx (2 x 1 mL), with a THF / Tx mixture (2 : 1) in fractions of 1 mL 10 until the wash waters were colorless.  PMC (A) II1 was obtained as a brown powdery solid, which was stored at 5 ° C dispersed in 1 mL of 0.21% Tx.  ICP-MS: 0.26% w Pd.  IR (KBr): v2900-3000 (m, arC-H st), 1723 (C = 0 st), 1601 (m, arC = C st), 1493 (s, C = N st), 1450-1480 (m , arC = C st), 1260 cm-1 (CN St (amide)).  pH at the isoelectric point of potential Z: P. I.  = 4.8 [P. I. (Starting PMs) = 2.9].  TEM: 15 spherical magnetic particles of size between 160-230 nm.  N— H and El N "Br — Pd-Br k = 1 / IN PMC (A) 111 Example 35.  Preparation of PMC (A) I12.  The PMC (A) II2 was prepared as described for PMC (A) II1 in Example 34, but using the complex II (A) 2 described in Example 23.  They were obtained as a powdery brown solid, which was stored at 5 ° C dispersed in 1 mL of 0.21% Tx.  ICP-MS: 0.54% w Pd.  IR (KBr): v 2900-3000 (m, arC-H st), 1724 (C = 0 st), 1601 (m, 25 arC = C st), 1492 (s, C = N st), 1450-1480 (m, rC = C st), 1260 cm-1 (CN St (amide)).  pH at the isoelectric point of potential Z: P. one.  = 4.3 [P. I. (Starting PMs) = 2.9].  TEM: spherical magnetic particles of size between 190-270 nm.  49/ = N -N N H and N.  Br — Pd — Br 0 PMC (A) II2 Example 36.  Preparation of PMC (A) I13.  5 The PMCs (A) 113 were prepared as described for PMCs (A) 111 in Example 34, but using the complex 11 (A) 3 described in Example 24.  They were obtained as a brown, powdery solid, which is preserved at 5 ° C dispersed in 1 mL of 0.21% Tx.  ICP-MS: 0.36% w Pd.  IR (KBr): v 2900-3000 (m, arC-H st), 1723 (C = 0 st), 1601 (m, arC = C st), 1493 (s, C = N st), 1450-1480 ( m, arC = C st), 1260 cm-1 (CN St (amide)).  pH at 10 the isoelectric point of potential Z: P. ;.  = 4.6 [P. I. (Starting PMs) = 2.9].  TEM: spherical magnetic particles of tamarium between 180-250 nm.  N N.  H and s'Pr2Ph Br — Pd — Br H lPr2Ph N PMC (A) II3 15 Example 37.  Preparation of PMC (A) 1114.  PMC (A) 1114 were prepared as described for PMC (A) 111 in Example 34, but using the complex 111 (A) 4 described in Example 27.  They were obtained as a brown powdery powder, which Sc kept at 5 ° C dispersed in 1 mL of 0.21% Tx 20.  ICP-MS: 0.81% w Pd.  IR (KBr): v 2923-2970 (m, arC-H st), 1698 (C = 0 st), 1601-1650 (m, arC = C st), 1538 (s, C = N st), 1450- 1480 (m, arC = C st), 1272 cm-1 (CN St (amide)).  pH at the isoelectric point of potential Z: P. I.  = 6.2 [P. I. (Starting PMs) = 2.9].  TEM: spherical magnetic particles of size between 190-250 nm.  fifty_ _ e HN— N. , - 1 2 Br,) —N Pd> (7.  0_ Br ') - N / --- N.  HN— / 0 PMC (A) III4 Example 38.  Testing of catalytic activity of the PMCs of this invention in Suzuki-Miyaura reactions.  5 The catalytic tests were carried out in a glove box ("La petite" model 815-PGB of Plaslabs INC), in the absence of oxygen, in sterilized 1.5 mL Eppendorf single-use vials containing 1 mL of a suspension of the supported palladium catalyst (ii) in a 9: 1 mixture of an aqueous solution of 10 TritOnrm X405 at 0.21% by volume and TM :, the corresponding haloarene (4-bromine or 4-chlorotoluene), Phenylboronic acid (molar ratio with respect to haloarene 1: 1,2), potassium carbonate (molar ratio with respect to haloarene 1: 3) and naphthalene as internal standard (0.5 mmol).  In all cases 2.5 mg of PMCs were used and the amounts of the substrates were adjusted to reach a palladium load of 0.05 mol 15% [Pd] for the PMC (S1) 11-3 described in Examples 28 at 30 and 0.024 mol% [Pd] for the remainder described in Examples 31 to 37, with respect to haloarene.  These mixtures were sonicated in a bath for one minute (Elmasonic S40, 37 kHz sonication frequency).  Then the vials were placed inside the glove box on the support of a previously thermostated mechanical agitator (Bioshake iQ de Qlnstruments) with temperature control at 65 ° C for bromotoluene activation and at 80 ° C for chlorotoluene activation .  Once the vials were placed, the reaction time began to be measured.  The progress of the reaction was continued by periodically removing samples that were analyzed by gas chromatography (HP-5890 Series II Instrument chromatograph with flame ionization detector (FID); DB-WAX polar capillary column with a polyethylene glycol film of 0, 25 pm thick and 30 meters long and 0.25 mm in diameter; 250 ° C injector, 260 ° C detector, 180 ° C oven isothermal (bromotoluene) or 120 ° C isothermal for 5 min and temperature ramp at 60 ° C / min up to 200 ° C (chlorotoluene).  For GC-FID monitoring, 1 pL of the 51 was takensolution and diluted) in the reaction solvent to 10 pL, from there take) 1 pL which was injected directly.  The conversion is determined from the concentration of haloarene present in the reaction mixture, using the naphthalene peak as internal standard and relative to the calibration line determined for 4-iodotoluene.  The coupling product was identified by 1 H NMR.  All experiments were performed at least in duplicate.  Reaction targets were also made, without adding PMCs, to rule out possible false results caused by palladium contamination of substrates, bases, solvents or starting PMs without supported complex.  Table 3 collects the results obtained with the PMCs described in Examples 28 to 37.  10 Example 39.  Catalytic activity assays of the PMCs of this invention in Heck-Mizoroki reactions.  The catalytic tests were carried out in the manner described in Example 38, but with 15 4-iodotoluene, methyl acrylate (molar ratio with respect to haloarene 1: 1.2), triethylamine (molar ratio with respect to haloarene 1: 1 ) and naphthalene as internal standard (0.5 mmol), with the mechanical stirrer previously thermostated at 90 ° C and with the chromatograph configured as indicated in Example 38 for 4-bromotoluene.  Table 4 shows the results obtained with the PMCs described in Examples 28 to 37. Example 40.  Evaluation of the recyclability of the PMCs of this invention in coupling reactions of Suzuki-Miyaura and Heck-Mizoroki.  Once the reaction was over, the vials were placed within the magnetic field of a 25 neodymium magnet (Supermagnete) for 5 min in order for the PMCs to be deposited on the side of the Eppendorf oriented towards the magnet.  Subsequently, the solutions were decanted with the products and the resulting PMCs were washed with THF (5 x 1 mL) and Tx (5 x 1 mL; Tx = aqueous solution of TritonTm X405 at 0.21% v).  Next, 1 mL of Tx / THF (9: 1) 30 containing a new substrate mixture was added to the vial with the recovered MNPs in order to restore the initial reaction concentrations described in each case in Examples 38 and 39.  Once the reagents were added, proceed) AS indicated in each case in Examples 38 and 39.  The operation was repeated a dozen times (13 uses of the catalyst counting the initial reaction) always under the same conditions and same reaction time.  From Figure 35 to Figure 6 a selection of graphic representations of some of the kinetic profiles obtained for the PMC (Si) 112 described in Example 32, 52 is shown.PMC (A) II3 described in Example 36 and PMC (A) III4 described in Example 37 in Suzuki-Miyaura reactions with both 4-bromotoluene and 4-chlorotoluene which were carried out as described in Example 38  Figure 7 and Figure 8 show a selection of graphic representations of some of the kinetic profiles 5 obtained for the PMC (Si) I3 described in Example 30, PMC (Si) 112 described in Example 32, PMC (A) 113 described in Example 36 and PMC (A) III4 described in Example 37 in the reactions of Heck-Mizoroki with 4-iodotoluene which were carried out as described in Example 39.  10 Example 41.  Quantification of palladium leachate from the PMCs of this invention in coupling reactions of Suzuki-Miyaura and Heck-Mizoroki.  Quantitative analyzes of palladium have been carried out by ICP-MS (Inductively coupled plasma mass spectrometry) of the separated solutions 15 both in the initial reactions described in Examples 38 and 39 and in the successive reactions in the series of recycled described in Example 40.  The analyzes were carried out of the solutions separated after the first one (recycling n ° 0-1), the second (recycling n ° 1-2), the third (recycling n ° 2-3), the fourth to the twelfth combined (recycling n 3-11) and the third use of the catalyst (recycled n ° 12).  20 The palladium content of the PMCs recovered at the end of each recycle series was also quantified by ICP-MS.  In the quantification of palladium by ICP-MS, at least 3 independent analyzes have been carried out in an Agilent 7700x device (detection limit 1ppb (pg / L); sample injection mode: Helium 4.3 mL / minute; values accepted [RSD] under 10%).  The samples were prepared by taking a fraction of known mass of solid ° obtained by direct evaporation of the corresponding suspension or solution and dissolving it in acidified medium (nitric acid / hydrochloric acid 3: 1).  Table 5 shows an illustrative selection of the percentage of initial palladium found in separate solutions and that lost by some of the PMCs of this invention (specifically the PMC (Si) I12 described in Example 32, the 30 PMC (A) II3 described in Example 36 and the PMCs (A) III4 described in Example 37) in the initial Suzuki-Miyaura reactions and subsequent reuse described in Examples 38 and 40, respectively, together with the conversion decreases (always measured in each case at the same time of reaction) recorded in the consecutive reactions of each series and expressed in percentage points.  Table 6 shows an illustrative selection of the percentage of initial palladium found in separate solutions and that lost by some of the PMCs of this invention (specifically the 53PMC (S1) 13 described in Example 30, the PMC (Si) 112 described in Example 32, the PMC (A) II3 described in Example 36 and the PMC (A) III4 described in Example 37) in the reactions of Heck-Mizoroki initial and successive reuse described in Examples 39 and 40, respectively, together with the conversion decreases (measured in 5 cases always at the same time of reaction) recorded in the consecutive reactions of each series and expressed in percentage points ales  Example 42  Determination of the initial productivity and activity values (TON ° and TON, of cumulative productivity (TON, -) of average activity (TOFAv) and 10 of palladium content found in the products (in ppm mass) using the PMCs of this invention in coupling reactions of Suzuki-Miyaura and Heck-Mizoroki.  The TON ° values have been determined taking into account the molar relationship of the limiting substrate with the palladium incorporated with each PMC and the conversion reached at the time specified in each case (Table 7 to Table 9), in the reactions described in the Examples 38 and 39.  The TOF0 value for each PMCs is the relationship between the corresponding value of TON () and the time, expressed in hours, to achieve that productivity in the reactions described in Examples 38 and 39.  The TONT value for 20 each PMCs is the sum of the TON value () and the TON values recorded in each of the 12 reuses described in Example 40.  The TOFAv value for each PMCs is the arithmetic mean of the TOF0 and the TOF values recorded in each of the 12 reuses described in Example 40.  The content of palladium in the products after the 13 uses of each PMC has been determined taking into account the value of TONT 25 reached in each case, the molecular weight of the product obtained, the quantification described in Example 41 of the leaching of the metal at separate solutions of the PMCs in the recycles described in Example 40 and the initial metal charge used in each series.  The palladium content in the products is expressed in parts per million (ppm) as the ratio of metal masses found in the solutions and of the total product formed.  Table 7 shows the values found in the reactions of Suzuki-Miyaura with 4-bromotoluene for some of the PMCs of this invention, specifically the PMC (Si) I11-3, PMC (A) I11-3 and PMC (A) 1114 described in Examples 31 to 37.  Table 8 shows the values found in Suzuki-Miyaura reactions with 4-chlorotoluene for some of the PMCs of this invention, specifically 35 PMC (Si) 111-3, PMC (A) I11-3 and PMC (A) 1114 written in Examples 31 to 37.  Table 9 shows the values found in the reactions of Heck-Mizoroki with 4-iodotoluene 54for the PMCs described in Examples 28 to 37.  Example 43  Ana! Isis TEM of the PMCs of this invention and of the separate solutions with the catalytic products.  5 The PMCs of this invention described in Examples 28 to 37 have been inspected by TEM (Transmission Electron Microscopy), both before use in the activity tests described in Examples 38 and 39 and of the PMCs recovered at the end of series of recycles described in Example 40, as well as samples 10 prepared from the separate solutions in those recycled ones.  The TEM analyzes have been carried out using a JEOL JEM 2100 microscope that operates at a voltage of 200 kV, equipped with double inclination sample holder ± 42 / ± 300, with a resolution between 2.5 A points and an EDS microanalysis system ("x-ray energy dispersive spectrocopy") with an OXFORD INCA instrument.  Alternatively, a HITACHI H7650 microscope has been used that operates at a voltage of 120 kV, equipped with a GATAN camera of 11 Mpx resolution.  Two different procedures for preparing PMC samples were followed depending on the equipment used for the measurement.  For the JEOL JEM 2100 equipment, some milligrams of the corresponding PMCs were embedded in a low viscosity epoxy resin known as Spurr, which consists of four components: the resin itself (ERL 4206, 50 mL), plasticizer (DER 736, 30 mL), hardener (NSA, 130 nnL) and accelerator (DMAE, 2 mL).  The resin was allowed to cure and harden for two days, after which it was cut into very thin sheets by using an ultramicrotome (Reichert-Jung, Ultracut-E model. ).  These sheets were deposited on 3 mm diameter copper grids coated with carbon (400 mesh).  Alternatively, for the HITACHI H7650 microscope, the sample preparation is carried out) by preparing dispersions of the PMCs in methanol or water (5-10 pL, 0.25-0.5 rng / nnL) on 3 mm diameter copper gratings Coated with carbon (400 mesh) allowing deposition to occur by evaporation.  Samples of the separate catalytic solutions of the PMCs were analyzed interchangeably in one of the two equipment and their preparation was made by adding 5 drops of the catalytic solution on 3 mm diameter copper grids coated with carbon (400 mesh) leaving that deposition occurs by evaporation.  The absence of metallic palladium in the samples was determined by EDS, inspecting the existence of the characteristic emission lines of the L layer of this metal at 2.83 KeV (Lai) and 3.03 KeV (431).  The comparison and analysis of the images obtained from the PMCs, whole or cut with ultramicrotome, before and after their 55Using catalysis as described in Examples 38, 39 and 40, it is possible to verify that none undergo appreciable morphological changes and that no aggregates of metallic palladium are observed next to them or in the samples prepared from the solutions separated with the products at the end of each reaction.  BIBLIOGRAPHY "Guideline on the Specification Limits for Residues of Metal Catalyst or Metal Reagents", European Medicines Agency, 2008, Doc.  Ref.  EMEA / CHMP / SWP / 4446/2000.  de Vries, J.  G.  "Palladium-Catalysed Coupling Reactions", Top.  Organomet  Chem  2012, 42, 1-34.  Diez-Gonzalez, S. ; Marion, N. ; Nolan, S.  P.  "N-Heterocyclic Carbenes in Late Transition 15 Metal Catalysis", Chem.  Rev.  2009, 109, 3612-3676.  Baig, R.  B.  N; Varma; R.  S.  "Magnetically retrievable catalysts for organic synthesis", Chem.  Commun.  2013, 49, 752-770.  20 Shylesh, S. ; Schunemann, V. ; Thiel, W.  R.  "Magnetically Separable Nanocatalysts: Bridges between Homogeneous and Heterogeneous Catalysis", Angew.  Chem  Int.  Ed.  2010, 49, 3428-3459.  Stevens, P.  D. ; Li, G. ; Fan, J. ; Yen, M. ; Gao, Y.  "Recycling of homogeneous Pd catalysts 25 using superparamagnetic nanoparticles as novel soluble supports for Suzuki, Heck, and Sonogashira cross-coupling reactions", Chem.  Commun.  2005, 4435-4437.  Zheng, Y; Stevens, P.  D. ; Gao, Y.  "Magnetic Nanoparticles as an Orthogonal Support of Polymer Resins: Applications to Solid-Phase Suzuki Cross-Coupling Reactions", J.  Org.  30 Chem.  2006, 71, 537-542.  35 Stevens, P.  D. ; Li, G. ; Gardimalla, H.  M.  R. , Yen, M. ; Gao, Y.  "Superparamagnetic Nanoparticle-Supported Catalysis of Suzuki Cross-Coupling Reactions", Org.  Lett.  2005, 7, 2085-2088.  Yang, H. ; Li, G. ; Ma, Z.  "Magnetic core — shell-structured nanoporous organosilica 56microspheres for the Suzuki-Miyaura coupling of aryl chlorides: improved catalytic activity and facile catalyst recovery ", J.  Mater.  Chem  2012, 22, 6639-6648.  Yang, H. ; Wang, Y. ; Qin, Y. ; Chong, Y. ; Yang, Q. ; Li, G. ; Zhang, L. ; Li, W.  "One-pot 5 preparation of magnetic N-heterocyclic carbene-functionalized silica nanoparticles for the Suzuki-Miyaura coupling of aryl chlorides: improved activity and facile catalyst recovery", Green Chem.  2011, 13, 1352-1361.  Tyrrell, E. ; Whiteman, L. ; Williams, N.  "The synthesis and characterization of immobilized 10 palladium carbene complexes and their application to heterogeneous catalysis", J.  Organomet  Chem  2011, 696, 3465-3472.  Harjani, J.  R. ; Friteid, T. ; MacGillivray, L.  R. ; Singer, R.  D.  "Removal of metal ions from aqueous solutions using chelating task-specific ionic liquids", Dalton Trans.  2008, 4595-154601.  20 25 30 Bussetto, L. ; Cassani, M.  C. ; Femoni, C. ; Macchioni, A. ; Mazzoni, R. ; Zuccaccia, D.  "Synthesis, molecular structures and solution NMR studies of N-heterocyclic carbene-amine silver complexes", J.  Organomet  Chem  2008, 693, 2579-2591.  Ballarin, B. ; Busetto, L. ; Cassani, M.  C. ; Femoni, C. ; Ferrari, A.  M. ; Miletto, I. ; Caputo, G.  "Primary amino-functionalize N-heterocyclic carbene ligands as support for Au (i). - Au (i) interactions: structural, electrochemical, spectroscopic and computational studies of the dimolecular [Au2 (NH2 (CH2) 2imMe) 2] [NO3] 2 ", Dalton Trans.  2012, 41, 2445-2455.  Ohara, H. , 0, W.  W.  N. ; Lough, A.  J. ; Morris, R.  H.  "Effect of chelating ring size in catalytic ketone hydrogenation: facile synthesis of ruthenium (ii) precatalysts containing an N-heterocyclic carbene with a primary amine donor for ketone hydrogenation and a DFT study of mechanisms", Dalton Trans.  2012, 41, 8797-8808.  Chi, Y.  S. ; Lee, J.  K. ; Lee, S. -g; Choi, I.  S.  'Control of Wettability by Anion Exchange on Si / Si02Suilaces ", Langmuir 2004, 20, 3024-3027.  Trilla, M. ; Pleixats, R. ; Wong Chi Man; M. ; Bied, C.  "Organic-inorganic hybrid silica 35 materials containing imidazolium and dihydroimidazolium salts as recyclable organocatalysts for Knoevenagel condensations", Green Chem.  2009, 11, 1815-1820.  575 10 Borja, G. ; Monge-Marcet, A. ; Pleixats, R. ; PareIla, T. ; Cattoen, X. ; Wong Chi Man, M.  "Recyclable Hybrid Silica-Based Catalysts Derived from Pd — NHC Complexes for Suzuki, Heck and Sonogashira Reactions", Eur.  J.  Org.  Chem  2012, 3625-3635.  Berardi, S. ; Carraro, M. ; Iglesias, M. ; Sartorel, A. ; Scorrano, G. ; Albrecht, M. ; Bonchio, M.  "Polyoxometalate-Based N-Heterocyclic Carbene (NHC) Complexes for Palladium-Mediated C — C Coupling and Chloroaryl Dehalogenation Catalysis", Chem.  Eur.  J.  2010, 16, 10662-1066.  Kunze, K. ; Nyce, G. ; Guo, W.  "Methods of polymerizing silanes and cyclosilanes using N-heterocyclic carbenes, metal complexes having N-heterocyclic carbene ligands, and lanthanide compounds", PCT Int.  Appl.  2011, PCT / US2011 / 046155, W02013019208A1.  15 Ten-Barra, E. ; de la Hoz, A. ; Sanchez-Migallon, A. ; Tejeda, J.  "Phase transfer catalysis without solvent.  Synthesis of bisazolylalkanes ", Heterocycles 1992, 34, 1365-1373.  Organ, M.  G. ; O'Brien, C.  J. ; Kantchev, E.  TO.  B.  "Transition metal complexes of N-heterocyclic carbenes, method of preparation and use in transition metal catalyzed 20 organic transformations", CA Appl.  2007, C, A2556850A1).  25 Yang, H. ; Han, X. ; Li, G. ; Yunwei Wang, Y.  "N-Heterocyclic carbene palladium complex supported on ionic liquid-modified SBA-16: an efficient and highly recyclable catalyst for the Suzuki and Heck reactions", Green Chem.  2009, 11, 1184-1193.  Polshettiwar, V. ; Varma, R.  S.  "Pd — N-heterocyclic carbene (NHC) organic silica: synthesis and application in carbonecarbon coupling reactions", Tetrahedron 2008, 64, 4637-4643.  Corma, A. ; Gonzalez-Arellano, C. ; Iglesias, M. ; Perez-Ferreras, S. ; Sanchez, F.  30 "Heterogenized Gold (I), Gold (III), and Palladium (II) Complexes for C — C Bond Reactions", Syntleff 2007, 1771-1774.  Lee, S. -M. ; Yoon, H. -J. ; Kim, J. -H. ; Chung, W. -J. ; Lee, Y. -S.  "Highly active organosilane-based N-heterocyclic carbene-palladium complex immobilized on silica particles for the 35 Suzuki reaction", Pure App !.  Chem  2007, 79, 1553-1559.  58Karimi, B. ; Enders, D.  "New N-Heterocyclic Carbene Palladium Complex / Ionic Liquid Matrix Immobilized on Silica: Application as Recoverable Catalyst for the Heck Reaction", Org.  Lett.  2006, 8, 1237-1240.  5 Wang, H.  M.  J. ; Lin, I.  J.  B.  "Facile Synthesis of Silver (I) -Carbene Complexes.  Useful Carbene Transfer Agents ", Organometallics 1998, 17, 972-975.  Rosario-Amorin, D. ; Gaboyard, M. ; Clerac, R. ; Vellutini, L. ; Nlate, S. ; Heuze, K.  "Metallodendritic Grafted Core — Shell y-Fe20— Nanoparticles Used as Recoverable 10 Catalysts in Suzuki C — C Coupling Reactions", Chem.  Eur.  J.  2012, 18, 3305-3315 59HETEROGENEIZED NHC PALADIO COMPLEXES AND THEIR USES AS RECOVERY CATALYSTS SECTOR OF THE TECHNIQUE 5 The invention is based on the chemical and pharmaceutical sector, more specifically on catalysts for organic synthesis processes based on metal complexes, and more specifically on N-heterocyclic carbine complexes supported palladium, magnetically separable after use, reusable and resistant to metal leaching, and in use 10 in carbon-carbon coupling reactions.  STATE OF THE TECHNIQUE As a result of the easy access of the substrates to their active centers and to the modifiable and controllable environment of these, catalysts based on metal complexes are characterized by their high activity and selectivity in many chemical processes that are carried out in mild conditions in homogeneous phase.  However, at present the industrial use of homogeneous catalysis applied to the production of pharmaceuticals, agrochemicals and other products of fine chemicals, is quite limited.  The 20 main reasons for the above are, on the one hand, the cost of the complexes and, on the other, the greatest difficulty in separating them from the products compared to heterogeneous catalysts.  These obstacles are especially relevant with platinum group metal complexes (Pt, Pd, Ir, Rh, Os, Ru), on which, in addition, there are environmental and sanitary guidelines and regulations that drastically restrict the permissible levels of contamination by metals in many productions (e. g. , European Medicines Agency 2008).  There is, therefore, a huge potential market for metal catalysts that combine the advantages of homogeneous phase catalysts (i. and. , high activity and selectivity in 30 mild conditions) with those of the heterogeneous phase (i. and. , high productivity and easy recovery and recycling).  A general classification of the strategies that have been explored so far includes: multi-phase catalysis or confinement of the homogeneous catalyst in a different phase from the substrate and products, including aqueous phases, ionic liquids, supercritical fluids or fluorinated solvents; ii) use of 35 nanofiltration membranes with enlarged molecular weight catalysts by means of their immobilization to soluble supports such as dendrimeros, polinneros or polysisesquioxanes; 2 

权利要求:
Claims (1)
[1]
CLAIMS 1. Magnetic particles with supported palladium complexes of formula PMC (S1) 1, 5 characterized in that they have mono complexes (NHC) of formula I (Si), [Pd] [Pd] [Pd] [Pd] anchored on their surface [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] PMC (Si) 1 0, O-'Si; Ny N'R X — Pd-X L '._1 (SO-anchored 10 comprising: the covalent immobilization of complexes through siloxane bonds that act as anchoring group. Particles with diameters in the range of tens to hundreds of nanOnneters , preferably 100-500 nm, with a nucleus of an iron oxide, preferably maghemite, and by an inert coating of silica an N-heterocyclic carbene (NHC) ligand, derived from an N, N'-substituted imidazolium salt by an R group and a spacer, preferably coordinated by its carbon in position 2 to the palladium of the anchored complexes.- a spacer between the walking group and the NHC ligand that is defined by a chain length of n links that can be comprised between 1 and 4 carbons.an R group in the heterocycle that can be another anchoring spacer or an alkyl, aryl or alkylaryl group, containing between 1 and 20 carbon atoms, and can be substituted by groups without active protons such as halogen, sulfonate , carboxylate, ether, thioether, ketone, sulfoxide, ester, amide, nitrile. two X ligands linked to each palladium which can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, 60Substituted or unsubstituted arylOxide, beta-diketonate, thiolate. an L 'coordinated to palladium which is a neutral monodentate ligand with donor nitrogen, preferably a pyridine that can be substituted by alkyls or halides at any of its carbons. 5 2. Magnetic particles according to claim 1, characterized in that they are selected from: particles in which the supported complexes contain the descriptors R = methyl, X- = 1, n = 3 and L '= 4-picoline with the imidazole ring not substituted at 10 its carbons (PMC (Si) 11, described). Particles in which the supported complexes meet the descriptors R = mesityl, X- = 1, n = 3 and L '= 4-picoline with the imidazole ring unsubstituted on their carbons (PMC (Si) I2, described). particles in which the supported complexes retain the descriptors R = 2,6- 15 diisopropylphenyl, X- = r, n = 3 and L '= 4-picoline with the imidazole ring unsubstituted on their carbons (PMC (S1) 13, described). 3. Magnetic particles with supported palladium complexes of formula PMC (Si) II, characterized by having bis (NHC) complexes of formula II (Si), [Pd] [Pd] [Pd] [Pd] [ Pd] [Pd] [Pd] [Pd] [Pd] [Pd] PMC (Si) II [Pd]: o Foo; sit), -, NI) NN "0, 11 (SO-anchored -0, / == —0; Si41 „N„ TN, R —0 On X-Pd-X comprising: 25 the covalent immobilization of the complexes through siloxane bonds that act as anchoring group. - particles with diameters in the range from tens to hundreds of nanometers, preferably 100-500 nm, with a nude ° of an iron oxide, 61preferably nnaghemite, and by an inert coating of silica. - two NHC ligands and two X ligands coordinated to the palladium of each anchored complex as defined in claim 1. 5 4. Magnetic particles according to claim 3, characterized in that they are selected from among: particles in which the supported complexes meet the descriptors R = methyl, X- = Br- and n = 3 with the imidazole ring unsubstituted at its carbons (PMC (S1) 111, described). 10 particles in which the supported complexes combine the descriptors R = mesityl, X- = Br- and n = 3 with the imidazole ring unsubstituted on their carbons (PMC (S1) 112, described). particles in which the supported complexes meet the descriptors R = 2,6-diisopropylphenyl, Br- = 1 and n = 3 with the unsubstituted imidazole ring at its 15 carbons (PMC (S1) 113, described). 20 5. Magnetic particles with supported palladium complexes of formula PMC (Si) 111, characterized by having bis (NHC) chelate complexes of formula III (Si), [Pd] [Pd] [Pd] [Pd] anchored on their surface [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] PMC (Si) III 0 OSi a)) --- N Pd (>) 15 Xl I-0 in III ( Si) -anchored comprising: the covalent immobilization of the complexes through siloxane bonds that act as an anchoring group. particles with diameters in the range of tens to hundreds of nanometers, preferably 100-500 nm, with a nucleus of an iron oxide, preferably maghemite, and by a coating of silica. 625 - two NHC ligands and two palladium-coordinated X ligands of each anchored complex as defined in claim 1, but in which the R group of the heterocycles is an alkyl chain that bridges the two NHC ligands, with a chain length of n 'links that can be between 1 and 3 carbons. 6. A process for synthesizing the particles of formulas PMC (S1) 1, PMC (S1) 11 and PMC (Si) III, defined in claims 1 to 5, comprising: the use of commercial magnetic particles of diameters in the range from 10 tens to hundreds of nanometers, preferably 100-500 nm, with a nude ° of an iron oxide, preferably maghemite, and by a coating of silica. their dispersion in organic solvents, or preferably in a hydroalcoholic medium in the presence of small amounts of non-ionic surfactants with high hydrophilic-hydrophobic balance (HLB> 15, used even below their critical micellar concentration). a slow addition of an alcoholic solution of the complex, I-111 (Si), to be immobilized so that a condensation reaction takes place between the surface silanols of the silica and the trialkoxysilyl groups present in the complexes before their immobilization. - constant mechanical agitation. a sequence of washes that consists of trapping the PMC (S1) 1-111 with an external 'man and separating them by decanting from the solutions. 25 7. Magnetic particles with supported palladium complexes of formula PMC (A) I, characterized by having mono complexes (NHC) of formula 1 (A), 53 anchored on their surface[Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] PMC (A) 1 2 H r == NNN f); 1 Y 1: 1/0 X — Pd-X 1 comprising: - the covalent immobilization of the complexes through amide bonds that act as anchoring group. Particles with diameters in the range of tens to hundreds of nanometers, preferably 100-500 nm, with a nude degree of an iron oxide, preferably maghemite, and by a coating of cross-linked polystyrene functionalized with carboxylic groups. 10 one NHC ligand, two X and one L 'ligands coordinated to the palladium of each anchored complex as defined in claim 1. 8. Magnetic particles with supported palladium complexes of formula PMC (A) II, characterized in that they have anchored in their surface complex bis (NHC) of formula II (A), [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] [Pd] FeO [Pd] PMC (A) II ----- 2 Lyr-INyN_R [Pd] 0 X — Pd-X ............,% 0 r1 / 4 0 in N NIR [Pd] ---- 1.11 H, = - • 1- [Pd] - ---- II (A) -anchored .._ comprising: 20 - the covalent immobilization of complexes through amide bonds that 545 act as an anchoring group. diarymeter particles in the range of tens to hundreds of nanometers, preferably 100-500 nm, with a node of an iron oxide, preferably maghemite, and by a cross-linked polystyrene coating functionalized with carboxylic groups. two NHC ligands and two X ligands coordinated to the palladium of each anchored complex as defined in claim 1 9. Magnetic particles according to claim 8, characterized in that they are selected from those described here: - particles in which the supported complexes gather the descriptors R = methyl, X = Br and n = 2 with the imidazole ring unsubstituted on their carbons (PMC (A) 111, described). particles in which the supported complexes meet the descriptors R = 15 mesityl, X = Br and n = 2 with the imidazole ring unsubstituted on their carbons (PMC (A) II2, described). particles in which the supported complexes meet the descriptors R = 2,6-diisopropylphenyl, X = Br and n = 2 with the imidazole ring unsubstituted at their carbons (PMC (A) II3, described). 20 25 10. Magnetic particles with supported palladium complexes of formula PMC (A) III, characterized by having bis (NHC) chelate complexes of formula III (A), [Pd] [Pd] [Pd] [Pd, anchored on their surface ] „-, ---- 2 [Pd] [Pd]„ ,,, [Pd] [Pd] [Pd] [Pd] PMC (A) III comprising: 65 '' - „0 111 (A) -anchoredthe covalent immobilization of the complexes through amide bonds that act as an anchoring group. particles with diameters in the range of tens to hundreds of nanOmeters, preferably 100-500 nm, with a nude ° of an iron oxide, preferably maghemite, and by a coating of cross-linked polystyrene functionalized with carboxylic groups. two NHC ligands and two palladium-coordinated X ligands of each anchored complex as defined in claim 1, but in which the R group of the heterocycles is an alkyl chain that acts as a bridge between the two NHC ligands, with a length chain of n 'links that can be comprised between 1 and 3 carbons. 11. Magnetic particles according to claim 10, characterized in that they are selected from: 15 - particles in which the supported complexes meet the descriptors n = 2, n '= 1 and X = Br with the imidazole ring unsubstituted in its carbons (PMC (A) III4, described). 12. A process for synthesizing the particles of formulas PMC (A) I, PMC (A) II and PMC (A) III, defined in claims 7 to 11, comprising: the use of commercial magnetic particles of diameters in the range from tens to hundreds of nanometers, preferably 100-500 nm, with a core of an iron oxide, preferably maghemite, and by a cross-linked polystyrene coating functionalized with carboxylic acid groups (density of COOH groups 300 pmol / g). their dispersion in a hydroalcoholic medium in the presence of small amounts of nonionic surfactants with a high hydrophilic-hydrophobic balance (HLB> 15, used below their critical micellar concentration). 30 the addition of a solution in a very polar solvent of the complex, 1-111 (A), to be immobilized, in the presence of a carbodiimide as a coupling agent so that a condensation reaction occurs between the acid groups of the coating and the groups primary amine present in the complexes prior to their immobilization. 35 constant mechanical agitation - a sequence of washes consisting of trapping PMC (S1) 1-111 with a magnet 665 external and separate them by decantation of the solutions. 13. Use of magnetic particles according to claim 1 as a catalyst in carbon-carbon coupling reactions. 14. Use of magnetic particles according to claim 3 as a catalyst in carbon-carbon coupling reactions. 15. Use of magnetic particles according to claim 5 as a catalyst in 10 carbon-carbon coupling reactions. 16. Use of magnetic particles according to claim 7 as a catalyst in carbon-carbon coupling reactions. 15 17. Use of magnetic particles according to claim 8 as a catalyst in carbon-carbon coupling reactions. 18. Use of magnetic particles according to claim 10 as a catalyst in carbon-carbon coupling reactions. 19. Use according to any of claims 13 to 18, wherein the magnetic particles are selected from: PMC (S1) particles 11. PMC particles (Si) 12. 25 PMC (S1) particles 13. PMC (S1) 111 particles. PMC particles (S1) 112. PMC (S1) particles 113. PMC (A) I11 particles. 30 PMC (A) I12 particles. PMC (A) I13 particles. PMC (A) II particles14. 20. A process to use the particles of formulas PMC (Si) I, PMC (Si) II and 35 PMC (Si) III, defined in claims 1 to 5, and of formulas PMC (A) I, PMC (A) II and PMC (A) III, defined in claims 7 to 11, comma 67Recyclable catalysts in carbon-carbon coupling reactions, comprising: the use of an aqueous medium in the presence of small amounts of non-ionic surfactants with high hydrophilic-hydrophobic balance (HLB> 15.5 used below their critical micellar concentration) to disperse the particles and reagents. the use of mild conditions and low loads of palladium catalyst. constant mechanical agitation. the separation at the end of the catalytic reaction of the magnetic particles of the solutions with the products with the help of an external man and by decanting the solutions. the recycling of magnetic particles through the sequence of separation-washing-reuse of the same. 68

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公开号 | 公开日

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ES2555613B2|2016-04-22|

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WO2015197890A1|2015-12-30|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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CN102091657A|2011-01-04|2011-06-15|黑龙江省科学院石油化学研究院|Method for preparing magnetic double-carbene palladium ligand catalyst and using method thereof|

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CN106732555B|2016-11-25|2018-06-05|江西省汉氏贵金属有限公司|The alpha-alkylization of ketone and alcohol reaction palladium carbon catalyst and preparation method thereof|

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ES201400505A|ES2555613B2|2014-06-26|2014-06-26|NHC heterogeneized palladium complexes and their uses as recoverable catalysts|ES201400505A| ES2555613B2|2014-06-26|2014-06-26|NHC heterogeneized palladium complexes and their uses as recoverable catalysts|

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PCT/ES2015/070234| WO2015197890A1|2014-06-26|2015-03-27|Heterogenised palladium nhc complexes and uses thereof as recoverable catalysts|