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    • 专利摘要:
    Molecular trap for the selective capture of carbon disulfide and other related toxic compounds consisting of metal complexes belonging to the last groups of transition elements capable of forming plano-squared complexes, stabilized by a chelating ligand that occupies three of the coordination positions of the metal, while the fourth coordination position is occupied by a pyrazolate ligand, or the like containing free nitrogen and potentially donors. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2710793A1
    申请号:ES201731251
    申请日:2017-10-24
    公开日:2019-04-26
    发明作者:Perez Juan Campora；Ramirez Pilar Palma；Segura Elena Avila；Garrido Mercedes Luque
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0001]
    [0002] Molecular trap for the selective capture of carbon disulfide and other related toxic compounds
    [0003]
    [0004] BACKGROUND OF THE INVENTION
    [0005]
    [0006] Carbon disulfide (CS2), and other related substances such as carbon oxysulfide (COS) are very toxic substances whose molecular structure is closely related to that of CO2. In particular, carbon disulfide is a substance widely used in the chemical industry, and its disposal of products and effluents is important. Thus, the techniques that allow the selective elimination of CS2 or COS in the presence of CO2 can have a practical interest.
    [0007]
    [0008] In recent years, considerable interest has been generated in the capture of CO2 and other small molecules by means of Frustrated Lewis Pairs (FLP). This type of compounds, in which acid and basic Lewis centers coexist, usually have a high affinity for CO2, but are usually less reactive towards CS2 and its heavier analogues.
    [0009]
    [0010] Particularly, the compound 2,6-bis ((di-tert-butylphosphino) methyl) phenyl) (2-methyl-1H-imidazol-1-yl) nickel has been described in Chemistry-A European Journal, 2012, 18 (22), 6915-6927, where nickel complexes are synthesized on the ligand 1,3-bis (diisopropylphosphino) phenyl (PCP). All new complexes have been reacted with carbon dioxide.
    [0011]
    [0012] Likewise, the complex {2,6-Bis [(2,6-diisopropylphospharyl) oxy] -4-fluorophenyl- K 3 P, C1, P} ( 1H-pyrazole- K N 2) nickel (II) hexafluorophosphate has been synthesized (Acta Crystallographica Section E: Structure Reports Online, 2012, 68 (10), m1282-m1283), although its potential application has not been described nor is it suggested reactivity by CS2 or similar compounds.
    [0013] DESCRIPTION OF THE INVENTION
    [0014]
    [0015] New metal complexes belonging to the last groups of transition elements capable of forming plane-squared complexes (eg Ni (II), Pd (II), Co (I), Rh (I)), have been designed. stabilized by a chelator, or clamp-type ligand, occupying three of the metal's coordination positions, while the fourth coordinate position is occupied by a pyrazolate ligand, or the like containing free and potentially donor nitrogen (e.g. , indazoles, triazoles or amidinates), which is coordinated through one of its nitrogen atoms, leaving the second free.
    [0016]
    [0017] Thus, the complex has an acid center (the metal atom) and a basic center (the pyrazole nitrogen), which are separated by a distance similar to the size of the CS2 molecule (Figure 1). The calcofila nature of the metal center (that is to say, afln to the sulfur) can explain that this compound reacts with CS2, whereas the Classic Frustrated Lewis Pairs (FLP), of oxoflicic type, react easily with the CO2. The absence of reactivity to CO2 is essential for its practical use, since the selective fixation of CS2 or other related molecules such as COS, can find other applications, such as, for example, selective detectors, since it entails a color change (Figure 2). ).
    [0018]
    [0019] In addition, these ligands are stable at a temperature of 150 ° C in air. They are also stable against oxygen and moderate humidity levels. This chemical and thermal stability is given by the tridentate ligand that supports the structure that also guarantees the square-planar coordination in the metal atom and prevents the formation of products in which the basic center and the acid are mutually deactivated.
    [0020]
    [0021] In a first aspect, the present invention relates to a compound of formula (I)
    [0022]
    [0023]
    [0024] optionally charged where n is selected from 0 to 1, and A "is a counterion, preferably sodium, potassium or thallium, comprising:
    [0025]
    [0026] a) a metal M that is selected from Ni (II), Pd (II), Co (I), Rh (I);
    [0027] b) a tridentate chelating ligand where:
    [0028] X is selected from O, S, NR 'and CH2, where R' is selected from H or C1-C4 alkyl;
    [0029] And it is a donor group that is selected from among P (iPr) 2, P (* Bu) 2, P (Ph) 2, N (Me) 2, S (Ph), S (tBu), S (Me), and Se (Ph);
    [0030] Z is selected from C and N; Y
    [0031] R1, R2, R3 are independently selected from H, C1-C4 alkyl and halogen; Y
    [0032] c) a diazolate ligand L derived from its corresponding heterocyclic bases which are selected from pyrazole, imidazole, indazole, and triazole, optionally substituted by a C 1 -C 4 alkyl, C 6 -C 10 aryl, OR ', NR 2, halogen, and amino, and where R 'is selected from C1-C4 alkyl and C6-C10 aryl.
    [0033]
    [0034] In a preferred embodiment, metal M is selected from Ni (II) and Pd (II), and more preferably M is Ni (II).
    [0035]
    [0036] In another preferred embodiment, X is selected from O and CH2, and more preferably X is CH2.
    [0037]
    [0038] In another preferred embodiment, Y is P (iPr) 2.
    [0039] In another preferred embodiment, L is selected from 3-methylpyrazole (MePz), 3,5-dimethylpyrazole (Me2Pz), imidazole (Iz), 2-methylimidazole (MeIz), 4-methylimidazole (Me'Iz), and 1.2. 4- triazole (Tz). More preferably L is 3,5-dimethylpyrazole.
    [0040]
    [0041] In another preferred embodiment, Z is C, and the compounds have the formula (la)
    [0042]
    [0043]
    [0044]
    [0045]
    [0046] where
    [0047] M is selected from Ni (ll), Pd (ll), Co (l), Rh (l);
    [0048] X is selected from O, S, NR 'and CH2, where R' is selected from H or C1-C4 alkyl;
    [0049] And it is a donor group that is selected from among P (iPr) 2, P ('Bu) 2, P (Ph) 2, N (Me) 2, S (Ph), S (' Bu), S (Me) , and Se (Ph);
    [0050] R1, R2, R3 are independently selected from H, C1-C4 alkyl and halogen; and L is a diazolate ligand which are selected from pyrazole, imidazole, indazole, and triazole, optionally substituted by a C1-C4 alkyl, C6-C10 aryl, OR ', NR'2, halogen, and amino, and where R' it is selected from C1-C4 alkyl and C6-C10 aryl.
    [0051]
    [0052] In a more preferred embodiment, the metal M is selected from Ni (ll) and Pd (ll), and more preferably M is Ni (ll).
    [0053]
    [0054] In another more preferred embodiment, X is selected from O and CH2, and more preferably X is CH2.
    [0055]
    [0056] In another more preferred embodiment, Y is P (iPr) 2.
    [0057]
    [0058] In another more preferred embodiment, L is selected from 3-methylpyrazole (MePz), 3,5-dimethylpyrazole (Me2Pz), imidazole (Iz), 2-methylimidazole (Melz), 4-methylimidazole (Me'Iz), and 1.2 .4- triazole (Tz). More preferably L is 3,5-dimethylpyrazole.
    [0059] In another preferred embodiment, Z is N, and the compounds have the formula (Ib)
    [0060]
    [0061]
    [0062]
    [0063]
    [0064] where
    [0065] M is selected from Ni (II), Pd (II), Co (I), Rh (I);
    [0066] X is selected from O, CH2, and S;
    [0067] And it is a donor group that is selected from among P (iPr) 2, P (tBu) 2, P (Ph) 2, N (Me) 2, S (Ph), S (tBu), S (Me), and Se (Ph);
    [0068] R1, R2, R3 are independently selected from H, C1-C4 alkyl and halogen; L is a diazolate ligand which is selected from pyrazole, imidazole, indazole, and triazole, optionally substituted by a C 1 -C 4 alkyl, C 6 -C 10 aryl, OR ', NR 2, halogen, and amino, and wherein R' is select from C1-C4 alkyl and C6-C10 aryl; and A- is a counterion, preferably sodium, potassium or thallium.
    [0069]
    [0070] In a more preferred embodiment, metal M is selected from Ni (II) and Pd (II), and more preferably M is Ni (II).
    [0071]
    [0072] In another more preferred embodiment, X is selected from O and CH2, and more preferably X is CH2.
    [0073]
    [0074] In another more preferred embodiment, Y is P (iPr) 2.
    [0075] In another more preferred embodiment, L is selected from 3-methylpyrazole (MePz), 3,5-dimethylpyrazole (Me2Pz), imidazole (Iz), 2-methylimidazole (MeIz), 4-methylimidazole (Me'Iz), and 1 , 2,4-triazole (Tz). More preferably L is 3,5-dimethylpyrazole.
    [0076]
    [0077] The term "halogen", as understood in the present invention, includes fluorine, chlorine, bromine and iodine.
    [0078] The term "alkyl" refers to a straight or branched, saturated hydrocarbon chain having from 1 to 4 carbon atoms.
    [0079]
    [0080] The term "aryl" refers to an aromatic, monoclonal or polycyclic ring, having 6 to 10 carbon atoms.
    [0081]
    [0082] In the present invention, "ligand chelator or clamp type" is defined as a ligand capable of establishing two or more simultaneous junctions with the coordination nucleus. Particularly the chelating ligands of the invention occupy three of the coordinate positions of the metal, therefore they are called tridentates.
    [0083]
    [0084] In a second aspect of the invention, the synthesis of the compounds of general formula (I) is carried out by reacting equivalent amounts of the metal precursor complex and the corresponding diazolate, as shown in the following scheme
    [0085]
    [0086]
    [0087]
    [0088]
    [0089] Where R1, R2, R3, X, Y, Z, M and A are defined as described above, and X is a halogen, preferably bromine or chlorine.
    [0090]
    [0091] A third aspect of the invention is the use of the compound of formula (I), (la) or (Ib), as defined above, for the fixation and / or detection of CS2.
    [0092]
    [0093] A fourth aspect of the invention relates to a device for the fixation and / or detection of CS2, which comprises the compound of general formula (I), (a) or (Ib), as defined above.
    [0094]
    [0095] Throughout the description and the claims the word "comprises" and its variants do not intend to exclude other technical characteristics, additives, components or Steps. For those skilled in the art, other objects, advantages and characteristics of the invention will be apparent in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0096]
    [0097] BRIEF DESCRIPTION OF THE FIGURES
    [0098]
    [0099] FIG. 1. Representative diagram of the CS2 binding reaction by the compound ( 4b ) of the invention.
    [0100]
    [0101] FIG. 2. Qualitative test showing the color changes associated with the reactions of the 4b (Tube 1), 5b (Tube 2) or 6b (Tube 3) complexes with CS2 at different reaction times, t = 0 (A ), t = 1 min (B), t = 4 min (C) and t = 1 h (D). Approximate concentrations: [Ni]: 0.05 M, [CS2]: 0.15 M.
    [0102]
    [0103] FIG. 3. Comparison of the UV-Vis spectra (350-700 nm) in solution (CH2Cl2, [Ni] = 10-4 M) of the complex derivatives [(PCP) Ni-DMPz] ( 4b ) and [(PCP) Ni -SC (S) -DMPz] ( 7b ) (right) and [(POCOP) Ni-DMPz] ( 5b ) and [(POCOP) Ni-SC (S) -DMPz] ( 8b ).
    [0104]
    [0105] FIG. 4 Spectra difference that show the increase of the molar extinction coefficient when passing from the corresponding dimethylpyralate complexes to the corresponding adducts with CS2. The spectra of 7b (a) and 8b (b) were recorded in the presence of CS2 (10% V: V) to avoid their dissociation.
    [0106] EXAMPLES
    [0107]
    [0108] The invention will be illustrated below by means of tests carried out by the inventors, which show the effectiveness of the product of the invention.
    [0109]
    [0110] All the operations have been carried out under an inert atmosphere, using vacuum or dry chamber techniques. The solvents were distilled under suitable drying agents immediately before use. The NMR spectra were recorded on Bruker equipment, models DPX-300, DRX-400, or Advance III-400. The IR spectra were recorded in a Tensor 27 spectrophotometer, and the UV-Vis spectrophotometers in a Perkin-Elmer spectrophotometer, lambda 1200 model. Elemental analyzes (CHN) were performed in the Elemental Analysis Service of the IIQ, in a LECO analyzer TruSpec CHN.
    [0111]
    [0112] Example 1. Synthesis of the starting products
    [0113]
    [0114] The starting complexes [(PCP) NiBr] ( 1 ). [(POCOP) NiBr] ( 2 ) and [PNP) NiBr] + Br- ( 3-Br ) were prepared using our own improved versions of methods described in the literature [compounds 1 and 3 : Shih, W.-C .; Ozerov, OV Organometallics, 2015 , 34, 4951; compound 2: Vabre, B .; Lindeperg, F .; Zargarian, D. Green Chem. 2013 , 15, 3188] that allow its obtaining in a single stage, starting from metallic nickel powder (Ni (0)) and commercially available reagents. The improvements in the synthesis of the complex complexes 2 and 3 refer above all to the increase in scale and do not alter the procedures described in the bibliography. The improved procedure for the synthesis of complex 1 is described below: In a thick-walled glass ampoule, with a capacity of 500 mL, provided with a PTFE stopcock and a sufficiently powerful magnetic stirring bar, a solution is mixed consecutively. a, α'-dibromo-m-xylene (7.92 g, 30 mmol) in CH 3 CN (120 mL), nickel powder (0.73 g, 12.5 mmol), chlorodiisopropylphosphine (ClP (iPr) 2 1.6 mL , 10 mmol) and 2,6-lutidine (0.58 mL, 5 mmol). The PTFE valve of the ampoule closes hermetically, and then it is submerged with its contents in an oil bath at 100 ° C for 48 h. During all this time a vigorous magnetic agitation is maintained that allows to keep the metal powder in suspension, while avoiding the sedimentation of the abundant saline precipitate that is formed as the reaction progresses. After the prescribed time, and after After cooling to room temperature, a sample of the solution is taken by its 31P {1H} NMR analysis, which should indicate that the chlorophosphine has disappeared completely. The mixture is transferred to a round bottom Schlenk flask of 250 mL capacity, using a special 3 mm internal diameter cannula. The volatile components are removed under vacuum and the residue is extracted with THF (3x50 mL). The extracts are filtered through a silica gel column 5 cm high, which is washed with the same solvent until the eluate liquid has hardly any color. The filtered liquid is collected in a 500 mL round bottom flask equipped with a glass key that allows connection to the line. Once the filtration is complete, the silica column is removed, the flask is closed with a hermetic plug, and its contents are brought to dryness under vacuum. The oily brown residue is extracted with Et2O (3x50 mL), and transferred with a cannula equipped with a paper filter cap and diatomaceous earth to a 250 mL Schlenk tube, where it is concentrated until the solution is found. saturated at ambient temperature. The mixture is cooled gradually (first at 4 ° C and then at -20 ° C) and allowed to stand at -20 ° C overnight. A first crop of crystals is obtained. The solution is filtered, partially concentrated and stored again in the freezer for a second crystallization. The crystals were washed with Et2O at -80 ° C and dried under vacuum. The product appears as red crystalline needles of [(iPrPCP) Ni-Br], which contain 10% of [(iPrPCP) Ni-Cl] (yellow small prisms), as confirmed in its spectrum of 31P {1H} ( 61.7 ppm for the product of Br, and 60.6 for the product of Cl). In practice, the presence of the Cl derivative does not imply any inconvenience for the use of this complex. Yield, 10.0 g, 21 mmol, 70%.
    [0115]
    [0116] The palladium derivative [(PCP) PdCl] ( 1 ' ) was obtained by a procedure described previously (Martlnez-Prieto, LM; Melero, C .; del Rio, D .; Palma, P .; Campora, J .; Alvarez, E .. Organometallics, 2012 , 31, 1425).
    [0117]
    [0118]
    [0119] Example 2. Synthesis of diazolate ligands in anionic form
    [0120]
    [0121] In this work, several complexes have been prepared by means of substitution reactions in which the halide ligand is displaced by an anionic diazolate ligand derived from the corresponding heterodclic bases. The heterocycles that have been investigated are: ( a ) 3-methylpyrazole; ( b ) 3,5-dimethylpyrazole; ( c ) imidazole; ( d ) 2-methylimidazole, ( e ) 4-methylimidazole, ( f ) 1,2,4-triazole. The corresponding anionic ligands ( a ) MePz "; ( b ) Me2Pz"; ( c ) Iz "; ( d ) Melz"; ( e ) Me'lz "; ( f ) Tz" were generated in solution in THF in the form of sodium, potassium or thallium salts by treatment with the appropriate base. In the following, the procedures used to generate said solutions are described. The quantities are mentioned by way of example, and will be adapted in each case according to the needs.
    [0122]
    [0123]
    [0124] Method 1. Generation of potassium diazolate for immediate use
    [0125]
    [0126] A solution of the corresponding diazolate (0.5 mmol) in about 10 mL of THF is stirred at -80 ° C. An equivalent amount (0.5 mmol) of potassium tert-butoxide dissolved in a similar volume of the same solvent (THF) is added thereto. The cooling bath is removed and the mixture is stirred until it reaches room temperature. It is assumed that the conversion is quantitative. This method is of general use, but has two drawbacks: i) Possible error in the concentrations, since small quantities are weighed and ii) a small amount of t-butanol is generated, which remains in the reaction medium.
    [0127]
    [0128] Method 2. Preparation of a mother solution 0.5 M sodium diazolate in THF
    [0129]
    [0130] This method is convenient for pyrazolates, but is not practical with imidazolates or triazolates, due to the low solubility of their sodium salts, which precipitate partially in THF.
    [0131]
    [0132] In a 250 mL three-necked flask equipped with reflux condenser with burner, inlet for nitrogen and magnetic stirrer, 2 g of NaH (83 mmol) are suspended in 50 mL. In the third mouth of the flask, a compensating pressure addition funnel is placed, charged with a dissolution of the corresponding heterocycle (50 mmol) in about 50 mL of THF, and the inlet of the flask is closed. The content of the funnel is added drop by drop over the solution of the flask, while the latter is shaken vigorously. As the reaction progresses, an effervescence due to hydrogen is produced, which is allowed to escape through the bubbler connected to the refrigerant. Once the addition is complete, stirring is continued until the hydrogen emission becomes negligible (2-3 hours). At this time the reflux condenser and the compensated pressure funnel are removed, and the flask is closed with glass plugs. Agitation is continued at room temperature overnight (about 16h) to ensure that the reaction is complete. The solution is then decanted and centrifuged to remove any remnant of the remaining NaH. The concentration of the solution is determined by retro-evaluation: 1 mL of solution is taken and poured into an Erlenmyer flask containing water and 1 mL of a standard solution of 0.1 N HCl. The excess HCl is then titrated with a solution. Freshly prepared NaOH, whose concentration (approximately 0.1 N) has been determined with respect to the HCl pattern. The procedure is repeated three times and the average of the three measurements is taken.
    [0133]
    [0134] Method 3. Generation of a thallium diazolate solution for immediate use
    [0135]
    [0136] This method is suitable for pyrazole derivatives that give rise to soluble thallium salts. A solution of the heterocycle (0.5 mmol) in 10 mL of THF and cooled to -80 ° C. Then, an equivalent amount of 0.5 M solution of thallium ethoxide in the same solvent (1 mL) is added. The mixture is allowed to reach the ambient temperature and is ready to be used immediately.
    [0137]
    [0138] Method 4. Preparation of thallium imidazolate as an insoluble solid reagent
    [0139]
    [0140] On dissolution of imidazole (0.69 g, 10 mmol) in 20 mL of THF, stirred at room temperature, 15.9 mL of a 0.63 M solution of thallium ethoxide in the same solvent are added dropwise. Stirring is continued for 30 min. The white precipitate, very fine, is separated by filtration, washed with 15 mL of diethylether and dried under vacuum for 1 hour. The yield is practically quantitative.
    [0141]
    [0142] Example 3. Synthesis of neutral diazolate complexes, 4 and 5
    [0143]
    [0144] These products are obtained by reacting equivalent amounts of the nickel and palladium precursor complex, and the corresponding diazolate. In general, the potassium, sodium or thallium salts can be used interchangeably. Next, significant examples of each of these methods are described.
    [0145]
    [0146]
    [0147]
    [0148] [(PCP) Ni-MePz], 4a. On a solution of Tl (MePz) (0.525 mmol) in 0.4 mL of THF (prepared according to procedure 3), which is stirred at -80 ° C, 0.5 mL of a 0.5 M solution is added. complex 1 in THF (0.5 mmol). The mixture is allowed to reach room temperature and stirring is continued at room temperature. After 30 minutes an abundant precipitate of thallium salts has formed, which is removed by centrifugation. The yellow solution is dried and the residue is extracted with hexane (10 mL). The extract is filtered and the solution is concentrated until there are indications that it is saturated. The solution is allowed to stand at -20 ° C for 24-48 h, until the product crystallizes, forming rhombohedral yellow blocks. The crystals are separated by filtration, washed with cold hexane and dried under vacuum. Rto., 143 mg. 0.3 mmol, 60%.
    [0149]
    [0150] 31 P {1 H} NMR (C6D6, 25 ° C, 160 MHz): 558.5 ppm.
    [0151] 1 H NMR (C6D6, 25 ° C, 400 MHz): 50.99 (dtv, 12H, 3 J hh «J * hp « 8.0 Hz, C H 3), 1.04 (dtv, 12H, 3 J hh «J * hp « 8.0 Hz, C H 3), 1.95 (m, 4H, C H ), 2.65 (s, 3H, C H ^ pz), 2.79 (tv, 4H, J hp = 4.0 Hz, C H 2), 6.38 (s, 1H, Car-4pz H ), 6.92 (d, 2H, 3 J hh = 8.0 Hz, mCar H ), 7.06 (t, 1H, 3 J h H = 8.0 Hz, pCar H ), 7.40 (s, 1H, Car-5pz H ).
    [0152] 13 C {1 H} NMR (C6D6, 25 ° C, 100 MHz): 5 14.5 (s, C H3-3 pz), 17.4 (s, C H3), 18.0 (s, C H3), 23 , 3 (tv, J * cp = 10.1 Hz, C H), 32.6 (tv, J * cp = 8.6 Hz, C H2), 103.2 (s, C ar-4pzH), 121 , 9 (tv, J CP = 8.0 Hz, m C arH), 125.2 (s, p C arH), 139.1 (s, C ar-5pzH), 147.4 (s, C ar- 3pz), 152.7 (tv, J * cr = 13.0 Hz, or C ar), 159.3 (t, 2 J cr = 16.8 Hz, / C ar).
    [0153] Elemental Analysis: Calculated for C24H40N2NiP2: C, 60.4; H, 8.45; N, 5.87, Found: C, 58.5; H, 8.55; N, 5.73.
    [0154]
    [0155] [(PCP) Ni-Me2Pz], 4b : A) with TlMe2Pz: Following an analogous procedure as described for compound 4a , this compound is obtained as orange crystals. Yield, 0.197 g, 0.4 mmol, 80%. B) with NaMe2Pz: Over a 0.25 M solution of compound 1 in THF (16 mL, 4 mmol), which is stirred at -80 ° C, 7.9 mL of 0.53 M NaMe2Pz solution in THF is added. (4.2 mmol, mother solution prepared by Method 2). The mixture is allowed to reach room temperature, and stirring is continued for a further half hour. The salts are separated by centrifugation and the solution is brought to dryness. The residue is extracted with hexane (3 x 20 mL). The combined extracts are filtered and the solution is concentrated until the appearance of crystalline solid on the walls is observed. The solution is cooled to 20 ° C for 24 h, after which the supernatant liquid is separated from the orange crystalline material. The crystals are washed with cold hexane and dried in vacuo. The mother liquors are concentrated and cooled successively, to obtain 2 - 3 additional product harvests, which are added to the previous one. Combined performance, Rto. Combined: 1.925 g, 3.9 mmol, 98%.
    [0156] 31 P {1 H} NMR (C6D6, 25 ° C, 160 MHz): 555.9 ppm.
    [0157] 1 H NMR (C 6 D 6, 25 ° C, 400 MHz): 50.97 (dtv, 12H, 3 JHH «J * HP« 8.0 Hz, C H 3), 1.06 (dtv, 12H, 3 J hh « J hr «8.0 Hz, C H 3), 1.90 (m, 4H, CH), 2.56 (s, 6H, C H ^ z), 2.80 (TV, 4H, J * hr = 4 , 0 Hz, C H 2), 6,14 (s, 1H, Car-4pz H ), 6,91 (d, 2H, J = 8.0 Hz, mCa H ), 7.05 (t, 1H,
    [0158] 3 J hh = 8.0 Hz, pCar H ).
    [0159] 13 C {1 H} NMR (C6D6, 25 ° C, 100 MHz): 5 15.7 (s, C H3-pz), 18.0 (s, C H3), 18.9 (s, C H3), 24 , 3 (tv, J * cr = 9.0 Hz, C H), 33.5 (tv, J * cr = 13.0 Hz, C H2), 103.9 (s, C ar-4pzH), 122 , 6 (tv, J cr = 8.0 Hz, m C arH), 126.2 (s, p C arH), 147.6 (s, C ar-5pz), 147.9 (s, C ar- 3pz), 152.5 (tv, J * CP = 12.3 Hz, or C ar), 159.2 (t, 2 J cr = 17.0 Hz, / C ar).
    [0160] Elemental Analysis: Calculated for C25H42N2NiP2: C, 61.12; H, 8.78; N, 5.95, Found, C, 61.21; H, 8.78; N, 5.95.
    [0161]
    [0162] [(PCP) Pd-Me2Pz], 4'b : Over a solution of compound 1 ' in THF (0.481 g, 1 mmol), which is stirred at -80 ° C, 6.5 mL of NaMe2Pz 0.154 solution is added. M in THF (1.0 mmol, mother solution prepared by Method 2). The mixture is allowed to reach room temperature, and stirring is continued for a further half hour.
    [0163] The salts are separated by centrifugation and the solution is brought to dryness. The residue is extracted with hexane (3 x 20 mL). The combined extracts are centrifuged and the solution is concentrated to about 4-5 mL. The solution is cooled to -20 ° C for 72 h, until the crystallization of the product is complete. The colorless crystals of 2'd are separated by filtration, washed with cold hexane and dried under vacuum. Yield, 240 mg, 89%.
    [0164]
    [0165] 31 P {1 H} NMR (CaDa, 25 ° C, 160 MHz): 557.6 ppm.
    [0166] 1 H NMR (CaDa, 25 ° C, 400 MHz): 0.97 (dtv, 12H, 3J-h «J * hp« 7.1 Hz, C H 3), 1.00 (dtv, 12H, 3Jhh «J * hp «7.3 Hz, C H 3), 1.91 (m, 4H, C H ), 2.61 (s, a ,, 6H, C « 3-pz), 2.88 (tv, 4H , J * hp = 4.2 Hz, C H 2), 6.26 (s, 1H, Car-4pz H ), 7.02 (d, 2H, 3J-h = 7.3 Hz, mCa H ), 7.09 (t, 1H, 3 Jhh = 7.3 Hz, pCar H ).
    [0167] 13C {1 H} NMR (C6D6, 25 ° C, 100 MHz): 5 14.9 (s, C -3-pz), 17.2 (s, C H3), 17.9 (s, C H3), 23.8 (tv, J * cp = 10.8 Hz, C H), 33.6 (tv, J * cp = 11.6 Hz, C H2), 101.8 (s, C ar-4pzH), 122.0 (tv, J cp = 10.8 Hz, m C arH), 124.9 (s, p C arH), 151.2 (tv, J * cp = 10.7 Hz, or C ar), 160.8 (s, / C ar).
    [0168] Elemental Analysis (%): Calculated for (C25H42N2P2Pd): C, 55.71; H, 7.85; N, 5.20, Found: C, 55.70; H, 7.94; N, 5.22.
    [0169]
    [0170] [(PCP) Ni-Iz], 4c. 0.499 g (0.5 mmol) thallium imidazolate, prepared as indicated in method 4, is suspended in 20 mL of THF and 1 mL of a 0.5 M solution of complex 1 is added . The mixture is stirred for 12 h, after which the solids are removed by centrifugation. The resulting solution is taken to dryness, and the residue is extracted with diethyl ether (3 x 20 mL). The combined extracts are filtered and concentrated until the formation of small amounts of crystalline solid is observed. The solution is allowed to stand for 24-48 h at -20 ° C. The product forms yellow crystals, which are filtered, washed with a hexane: ether 1: 1 mixture and dried under vacuum. Yield, 0.139 g, 0.3 mmol, 60%.
    [0171] 31 P {1 H} NMR (C6D6, 25 ° C, 160 MHz): 555.2 ppm.
    [0172] 1 H NMR (C6D6, 25 ° C, 400 MHz): 50.86 (dtv, 12H, 3J-h «J * hp« 8.0 Hz, C H 3), 0.88 (dtv, 12H, 3J-h «J * hp« 8.0 Hz, C H 3), 1.70 (m, 4H, C H ), 2.70 (TV, 4H, J - p = 4.0 Hz, C H 2), 6 , 87 (d, 2H, 3J-h = 8.0 Hz, mCa H ), 6.89 (s, 1H, Car-2imz H ), 6.95 (t, 1H, 3J-h = 8.0 Hz , pCar H ), 7.63 (s, 1H, Car-4imz H ), 7.82 (s, 1H, Car-5imz H ).
    [0173] 13C {1H} NMR (C6D6, 25 ° C, 100 MHz): 5 17.3 (s, C H3), 17.8 (s, C H3), 23.0 (tv, J * cp = 10.0 Hz, C H), 32.4 (tv, J * cp = 14.0 Hz, C H2), 122.0 (tv, J * cp = 9.0 Hz, m C arH), 124.4 (s) , C ar-2lmzH), 125.5 (S, p C arH), 129.9 (S, C ar-5imzH), 143.9 (S, C ar-4imzH), 155.6 (tv, J * CR = 13.0 Hz, O C ar), 158.3 (t, 2JcP = 16.0 Hz, / C ar).
    [0174] Elemental Analysis: Calculated for C23H38N2NiR2 H2O: C, 57.41; H, 8.38; N, 5.82; Found, C, 56.78; H, 8.30; N, 5.75.
    [0175]
    [0176] [(PCP) Ni-Melz], 4d. On a solution of potassium 2-methylimidazolate (0.52 mmol) in 10 mL of THF (prepared by Method 1), which is stirred at -80 ° C, 1 mL of a 0.5 M solution of the complex 1 in the same solvent. During the addition, the mixture turns orange. The mixture is allowed to reach room temperature, and agitation is continued for 30 min. The solvent is evaporated under reduced pressure, and the residue is extracted with diethyl ether (20 mL). After removing the salts by filtration, an equal volume of hexane is added, and the solution is concentrated under reduced pressure until the formation of solid particles indicates that it has reached a point close to saturation. The solution is allowed to stand at -20 ° C for several days, until the crystallization of the product is complete. The crystals, yellow in color, are separated by filtration, washed with hexane and dried under vacuum. Yield, 0.167 g, 0.35 mmol, 70%.
    [0177] 31 P {1 H} NMR (C6D6, 25 ° C, 160 MHz): 555.4 ppm.
    [0178] 1 H NMR (C 6 D 6, 25 ° C, 400 MHz): 50.75 (dtv, 6 H, 3 Jhh «J * hr« 7.6 Hz, C H 3), 0.82 (dtv, 6 H, 3 Jhh «J * hr «7.2 Hz, C H 3), 0.86 (dtv, 6 H, 3Jhh« J * hr «7.6 Hz, C H 3), 0.91 (dtv, 6 H, 3Jhh« J hr «7.2 Hz, C H 3), 1.72 (m, 4H, C H ), 2.70 (s, 4H, C H 2), 2.79 (s, 3H, C H 3 -imz ), 6.83 (s, 1H, Car-4imz H ), 6.85 (d, 2H, 3Jhh = 7.8 Hz, mC ^ H), 7.01 (t, 1H, 3Jhh = 6.0 Hz) , pCar H ), 7.58 (s, 1H, Car-5imz H ).
    [0179] 13C {1H} NMR (CaD6, 25 ° C, 100 MHz): 5.1.1 (s, C H ^ z), 17.0 (s, C H3), 18.0 (s, C H3), 23 , 0 (tv, J * cr = 9.8 Hz, C H), 23.4 (tv, J * cr = 9.8 Hz, C H), 32.4 (tv, J * cr = 13.3 Hz, C H2), 121.8 (tv, J * CR = 8.5 Hz, m C arH), 123.7 (s, C ar-2imz), 125.7 (s, p C arH), 129 , 9 (s, C ar-5imz), 144.1 (s, C ar-4imz), 151.8 (tv, J * CR = 12.3 Hz, OR C ar), 157.1 (s, / C ar).
    [0180] Elemental Analysis (%): Calculated for C24H40N2NiR2: C, 60.4; H, 8.45; N, 5.87, Found: C, 58.83; H, 8.79; N, 9.56.
    [0181]
    [0182] [(PCP) Ni-Me'Iz], 4e. On a solution of potassium 4-methylimidazolate (0.52 mmol) in 10 mL of THF (prepared by Method 1), which is stirred at -80 ° C, 1 mL of a 0.5 M solution of the solution is slowly added. complex 1 in the same solvent. During the addition, the mixture turns orange. The mixture is allowed to reach room temperature, and stirring is continued for 30 min. It evaporates solvent under reduced pressure, and the residue is extracted with diethyl ether (20 mL). The product 2e was obtained with practically quantitative yield by evaporating the solution to dryness as an orange-colored oil, which was not possible to crystallize, although its NMR spectra indicate that the only impurities are residues of the solvents used in the crystallization attempts.
    [0183] 31 P {1 H} NMR (C6D6, 25 ° C, 160 MHz): 556.5 ppm.
    [0184] 1 H NMR (C6D6, 25 ° C, 400 MHz): 50.87 (dtv, 12H, 3Jhh «J * hp« 7.1 Hz, C H3), 0.91 (dtv, 12H, 3Jhh «J * hp« 8.2 Hz, C H 3), 1.72 (m, 4H, CH), 2.69 (m, 4H, C H 2) and (s, 3H, C H i ^ mz), 6.70 ( s, 1H, Car-2imz H ), 6.88 (d, 2H, 3Jhh = 7.3 Hz, mCar H ), 7.03 (t, 1H, 3Jhh = 7.5 Hz, pCar H ), 7, 47 (s, 1H, Car-5imz H ).
    [0185] 13C {1H} NMR (C6D6, 25 ° C, 100 MHz): 5 15.1 (s, C H ^ z), 17.7 (s, C H3), 18.3 (s, C H3), 23 , 5 (tv, J * cp = 10.0 Hz, C H), 32.8 (tv, J * cp = 14.0 Hz, C H2), 121.9 (s, C ar-2imzH), 122 , 4 (tv, J * CP = 9.0 Hz, m C arH), 125.9 (s, p C arH), 128.7 (s, C ar-5imzH), 143.7 (s, C ar -4imz), 153.0 (tv, J * CP = 13.0 Hz, OR C ar), 158.8 (s, / C ar).
    [0186]
    [0187] [(PCP) Ni-Tz], 4f. On a solution of potassium 1,2,4-triazolate (0.52 mmol) in 10 mL of THF (prepared by Method 1), which is stirred at -80 ° C, 1 mL of an aqueous solution is slowly added. , 5 M of complex 1 in the same solvent. The mixture is allowed to reach room temperature, and stirring is continued for 30 min. The solvent is evaporated under reduced pressure, and the residue is extracted with diethyl ether (20 mL). After eliminating the salts by filtration, an equal volume of hexane is added, and the solution, of dark yellow color, is concentrated under reduced pressure until the formation of solid particles indicates that it has reached a point close to saturation. The solution is allowed to stand at -20 ° C for several days, until the crystallization of the product is complete. The crystals, yellow in color, are separated by filtration, washed with hexane and dried under vacuum. Yield, 0.150 g, 0.32 mmol, 65%.
    [0188]
    [0189] 31 P {1 H} NMR (C6D6, 25 ° C, 160 MHz): 559.8 ppm.
    [0190] 1 H NMR (C6D6, 25 ° C, 400 MHz): 50.89 (dtv, 12H, 3Jhh «J * hp« 7.0 Hz, C H 3), 1.00 (dtv, 12H, 3Jhh «J * hp "7.0 Hz, C H 3), 1.80 (m, 4H, C H ), 2.73 (TV, 4H, J hp = 4.0 Hz, C H 2), 6.90 (d, 2H, 3Jhh = 8.0 Hz, mCar H ), 7.05 (t, 1H, 3Jhh = 8.0 Hz, pCar H ), 8.08 (s, 1H, Car-3trz H ), 8.60 ( s, 1H, Car-5trz H ).
    [0191] 13 C {1 H} NMR (C6D6, 25 ° C, 100 MHz): 5 17.5 (s, C H3), 18.0 (s, C H3), 23.3 (tv, J * cp = 11.0 Hz, C H), 32.1 (tv, J * cp = 13.5 Hz, C H2), 122.1 (tv, J * cp = 8.8 Hz, m C arH), 125.6 (s, p C arH), 151.9 (s, C ar_3_5trzH), 151.8 (tv, J * cr = 12.3 Hz, or C ar), 157.1 (s, / C ar).
    [0192] Elemental Analysis (%) : Calculated for C22H37N3NiR2, C, 56.92; H, 8.03; N, 9.05, Found, C, 55.64; H, 8.24; N, 10.42.
    [0193]
    [0194] [(POCOP) Ni-Me2Pz], 5b . A solution of [(iRrROCOR) Ni-Cl] (0.890 g, 2.04 mmol) in
    [0195] toluene (15 mL) is cooled to -80 ° C and a solution of dimethylpyralate of
    [0196] sodium in THF (0.53 M, 4.24 mL, 2.24 mmol, prepared according to method 1). The
    [0197] mix while reaching room temperature, and continue for 30 minutes
    [0198] more. An orange suspension is obtained, which is brought to dryness and the
    [0199] Oily residue is extracted with hexane (20 mL). The solution is filtered, concentrated and
    [0200] It is allowed to crystallize stored at -20 ° C, obtaining orange crystals with
    [0201] block shape. Rt., 0.750 g, 1.51 mmol, 74%.
    [0202]
    [0203] 31 P {1 H} NMR (CD2Cl2, 25 ° C, 160 MHz): 5183.1 ppm.
    [0204] 1 H NMR (CD 2 Cl 2, 25 ° C, 400 MHz): 5 1.04 (dtv, 12H, 3 Jhh «J * hr« 8.2 Hz, C H 3), 1.35
    [0205] (dtv, 12H, 3Jhh
    [0206] 13 C {1 H} NMR (CD2Cl2, 25 ° C, 100 MHz): 513.9 (s, C H3-pz), 16.0 (s, C H3), 16.2 (s, C H3),
    [0207] 27.6 (tv, J * cr = 10.6 Hz, C H), 102.3 (s, C ar-4pzH), 104.7 (tv, J * cr = 5.8 Hz, m C arH) , 126.4
    [0208] (t, 2JCR = 21.9 Hz, / C ar), 128.9 (s, p C arH), 148.4 (s, a ,, C ar-3.5-pz), 169.1 (tv , J * CR = 9.9 Hz,
    [0209] oC ar).
    [0210] Elementary Analysis (%). Calculated for C 23 H 38 N 2 N i O 2 R 2, C, 55.79; H, 7.73; N, 5.66, Found, C, 56.09; H, 7.42; N, 5.77.
    [0211]
    [0212] Example 4. Synthesis of cationic diazolate [(NCN) Ni-Me2Pz] + [BPh4] -, 6b
    [0213]
    [0214] The synthesis of this complex requires changing the external anion of the precursor 3 B r , followed by the exchange of the internal anion with sodium dimethylpyralate.
    [0215]
    [0216]
    [0217]
    [0218]
    [0219] To a solution of [(iRrRNR) Ni-Br] Br ( 3-Br ) (1.01 g, 1.95 mmol) in CH2Cl2 (15 mL) was
    [0220] add a solution of NaBPh4 (671 mg, 1.95 mmol) in THF (10 mL). The color of the mixture changes from green to orange. It is brought to dryness and the residue is washed with THF to remove the NaBPh4 residues. Extract with CH2Cl2 (2x20 mL), filtering the solutions. The extracts are combined and the solvent is removed under vacuum, leaving an oily residue, which solidifies upon being washed with cold hexane. The hexane supernatant is filtered, and the solid is dried under vacuum. The product 3 BPh 4 is obtained as an orange powder. Yield, 1.510 g, 1.9 mmol, 97%.
    [0221]
    [0222] On a suspension of 100 mg of 3 BPh 4 (0.125 mmol) in 15 mL of THF (15 mL), which is stirred at -80 ° C, a solution of sodium 3,5-dimethylpyralate is added in THF (0, 27 M, 463 pL, 0.125 mmol). The color changes from orange to brown. The mixture is allowed to reach room temperature, and is brought to dryness. The remaining oil is extracted with 20 mL of CH2Cl2 and the resulting solution, orange-orange in color, is filtered to remove the salts. The solvent is again removed under vacuum, and the residue is stirred with Et 2 O, until it solidifies. The supernatant liquid is filtered, and the reddish-orange solid is dried under vacuum and crystallized by diffusion of Et2O in THF.
    [0223] Yield: crude, 74 mg 0.1 mmol, 73%; crystallized, 0.08 mmol, 66%.
    [0224]
    [0225] Analog and spectroscopic data for 3 BPh4:
    [0226] 31 P {1 H} NMR (CD2Cl2, 25 ° C, 160 MHz): 547.7 ppm.
    [0227] 1 H NMR (CD2Cl2, 25 ° C, 400 MHz): 5 1.24 (dtv, 12H, 3 JHH * J * HP * 8.5 Hz, CH3), 1.46 (dtv, 12H, 3 J hh * / hp * 8.9 Hz, CH3), 2.37 (m, 4H, CH), 3.16 (TV, 4H, J * hp = 3.7 Hz, CH), 6.87 (t, 4H, 3 J) hh = 7.5 Hz, pCaH (BPh4)), 7.01 (t, 8H, 3 J hh = 7.5 Hz, mCaH (BPh4)), 7.08 (d, 2H, 3 J hh = 7, 7 Hz, mCarH (PNP)), 7.35 (s, a, 8 H, oCaH (BPh4)), 7.57 (t, 3 J hh = 7.7 Hz, pCarH (PNP)).
    [0228] 13 C {1 H} NMR (CD 2 Cl 2, 25 ° C, 100 MHz): 5 17.4 (s, CH 3), 18.0 (s, CH 3), 23.7 (tv, J * cp = 12.6 Hz, CH), 33.2 (tv, J * cp = 9.4 Hz, CH2), 121.8 (s, pCarH (BPh4)), 123.2 (tv, J * cp = 5.1 Hz, mCarH ( PNP)), 125.7 (s, a ,, mCarH (BPh4)), 135.9 (s, oCarH (BPh4)), 140.8 (s, pCarH (PNP)), 163.8 (s, iCar) (BPh4)), 164.7 (vt, J * cp = 7.0 Hz, oCar (PNP)).
    [0229] Elemental Analysis (%): Calculated for C43H55BBrNNiP2: C, 64.78; H, 6.95; N, 1.76, Found, C, 64.83; H, 7.07; N, 1.93.
    [0230]
    [0231] Analog, spectroscopic and structural data for 6a:
    [0232] Molar weight: 811.39 g / mol.
    [0233] 31 P {1 H} NMR (CD2Cl2, 25 ° C, 160 MHz): 541.9 ppm.
    [0234] 1 H NMR (CD 2 Cl 2, 25 ° C, 400 MHz): 5 0.85 (dtv, 6 H, 3 J hh « J * hp « 8.2 Hz, C H 3), 0.87 (dtv, 6 H, 3 J hh « J hp « 8, 2 Hz, C H 3), 1,16 (dtv, 6 H, 3 J hh « J * hp « 7,7 Hz, C H 3), 1,33 (dtv, 6 H, 3 J hh « J hp « 8.2 Hz, 3H, C H 3), 2.08 (s, C H ^ pz) and (m, 2H, CH), 2.35 (s, C H 3-5pz) and (m, 2H, C H ), 3.10 (m, 4H, C H 2), 5.67 (s, 1H, Car-4pz H ), 6.86 (t, 4H, 3 J hh = 7.1 Hz, pCaH (BPh4)), 6.96 (d, 2H, 3 J hh = 7.9 Hz, m Car H (PNP)), 7.00 (t, 8 H, 3 J hh = 7.4 Hz, m Car H (BPh4)), 7.31 (s, a, 8 H, oCarH (BPh4)), 7.53 (t, 1H, 3 J hh = 7.8 Hz, p Ca H (PNP)).
    [0235] 13 C {1 H} NMR (CD2Cl2, 25 ° C, 100 MHz): 5 13.8 (s, C H3-3 pz), 14.7 (s, C H3-5 pz), 16.4 (s, C H3) , 16.5 (s, C H3), 17.1 (s, C H3), 17.4 (s, C H3), 22.6 (tv, J * cp = 11.5 Hz, C H), 23.2 (tv, J cp = 11.5 Hz, C H), 30.9 (tv, J cp = 10.3 Hz, C H2), 105.3 (s, C ar-4pzH), 122, 0 (s, p C arH (BPh4)), 122.9 (s, a ,, m C arH (PNP)), 125.9 (s, a ,, m C arH (BPh4)), 135.8 ( s, or C arH (BPh4)), 141.0 (s, p C arH (PNP)), 148.1 (s, C ar-3pz), 151.8 (s, C ar-5pz), 163, 9 (tv, J * CP = 5.9 Hz, O C ar (PNP)), 164.6 (s, / C ar (BPh4)).
    [0236] Calculated Elementary Analysis (C48Ha2BN3NiP2): C, 70.96; H, 7.69; N, 5.17.
    [0237] Experimental Elementary Analysis : C, 70.66; H, 7.75; N, 5.34.
    [0238]
    [0239] Example 5. Reaction of nickel pyrazolate complexes with CS2 and COS
    [0240]
    [0241] The complexes containing the anion Me2Pz ( 4b, 5b and 6b) react with CS2 and COS at room temperature, reversibly, with visible color changes. The reactions are very clean and give rise to a single product. None of the products studied reacts with CO2, so the presence of this gas does not interfere in the reactivity with other molecules.
    [0242]
    [0243]
    [0244] [(PCP) Ni-SC (S) Me2Pz], 7b . On a solution of complex 4b (0.100 g, 0.2 mmol) in hexane (5 mL), CS2 is added with a microsyringe (122.4 p, L, 2 mmol) at room temperature. After 30 seconds the color of the solution changes from the initial yellow to intense red, accompanied by the appearance of a solid, also red, in suspension. The solid is separated by filtration. The solution is concentrated and allowed to crystallize at -20 ° C. Blood-red needle-shaped crystals are obtained. Combined yield, 0.10 g, 0.18 mmol, 88%.
    [0245]
    [0246] 31 P {1 H} NMR (CaDa, 25 ° C, 160 MHz): 554.5 ppm.
    [0247] 1 H NMR (CaDa, 25 ° C, 400 MHz): 5.82 (m, 12H, C H 3), 0.98 (m, 12H, C H 3), 1.70 (s, 3H, C H 3-5pz), 1.89 (m, 4H, CH), 2.80 (s, a ,, 4H, C H 2), 3.01 (s, 3H, C « 3-3pz), 5.65 (s, 1H, Car-4pz H ), 6.87 (d, 2H, 3Jhh = 7.4 Hz, mCar H ), 7.00 (t, 1H, 3Jhh = 7.6 Hz, pCar H ).
    [0248] 13C {1H} NMR (C6D6, 25 ° C, 100 MHz): 512.6 (s, C H3-5pz), 17.9 (s, a ,, C H3), 18.7 (s, C H3- 3pz), 24.4 (s, a ,, C H), 35.1 (tv, J * cr = 11.8 Hz, C H2), 113.4 (s, C ar-4pzH), 121.6 (s, m C arH), 124.4 (s, p C arH), 144.6 (s, C ar-3pz), 149.5 (s, C ar-5pz) and (tv, J * cr = 12.8 Hz, or C ar), 161.8 (t, 2 Jcr = 17.3 Hz, / C ar), 210.2 (s, C S2).
    [0249] Elemental Analysis (%): Calculated for C26H42N2NiR2S2: C, 55.04; H, 7.46; N, 4.94; S, 11.30; Found: C, 55.32; H, 7.50; N, 4.92; S, 11.02.
    [0250]
    [0251] [(POCOP) Ni-SC (S) Me2Pz], 8b . This reaction has been studied by means of NMR spectroscopy, without proceeding to isolate the product. The complex [(iRrROCOR) Ni-3,5-dimethylpyrazole], 5b, (20 mg, 0.040 mmol) in C6D6 (0.5 mL) is dissolved in an NMR tube and its 1H and 31R spectra are recorded. Subsequently, carbon disulfide (10 p, L, 0.10 mmol) is added and the solution, initially yellow, turns red. The spectra are recorded again and the quantitative formation of a new product is observed. The spectra are consistent with the proposed structure.
    [0252]
    [0253] 31P {1H} NMR (CD2Cl2, 25 ° C, 160 MHz): 5181.8 ppm
    [0254] 1 H NMR (CD2Cl2, 25 ° C, 400 MHz): 5 1.08 (dtv, 12H, 3Jhh «J * hr« 6.9 Hz, C H 3), 1.21 (dtv, 12H, 3Jhh «J * hr «7.6 Hz, C H 3), 1.82 (s, 3H, C H ^), 2.31 (m, 4H, C H ), 2.89 (s, 3H, C H 3-pz) ), 6.15 (s, 1H, Car-4pz H ), 6.36 (d, 2H, 3Jhh = 7.9 Hz, mCar H ), 6.87 (t, 1H, 3Jhh = 7.9 Hz, pCar H ).
    [0255] 13C {1 H} NMR (CD2Cl2, 25 ° C, 100 MHz): 5 13.1 (s, C H3-pz), 16.8 (s, C H3), 17.3 (s, a ,, C H3 ), 18.6 (s, C H3-pz), 29.8 (tv, J * cr = 9.2 Hz, C H), 104.8 (tv, J * cr = 5.7 Hz, m C arH), 114.2 (s, C aMpzH), 127.2 (s, p C arH), 145.4 (s, C ar-pz), 151.1 (s, C ar-pz), 166.4 (t, 2Jcp = 9.9 Hz, / C ar), 210, 6 (s, CS2)
    [0256]
    [0257] [(PNP) Ni-SC (S) Me 2 Pz] + [BPh 4 ] ' , 9b . On a solution of [(iPrPNP) Ni-3,5-dimethylpyrazole] BPh4, 6b , (0.517 g, 0.64 mmol) in CH2Cl2 (1.5 mL) is added CS2 (383 ^ L, 6.4 mmol) with a microsyringe to room temperature. The dissolution, already initially red, evolves to a more intense color, which is reached 1 minute after the addition. The mixture is stirred for 30 minutes, after which volatile components are removed under vacuum. The residue, very dark red and slightly oily, is redissolved in 2 mL of CH2Cl2. A layer of hexane is deposited on this solution, and the solvents are allowed to diffuse at room temperature. Dark red needles are obtained, leaving in a few hours the solution practically colorless. Yield: 0.50 g, 0.56 mmol, 88%.
    [0258] 31 P { 1 H} NMR (CD2Cl2, 25 ° C, 160 MHz): 537.4 ppm.
    [0259] 1 H NMR (CD2Cl2, 25 ° C, 400 MHz): 5 0.84 (dtv, 6 H, 3 Jhh «J * hp« 8.3 Hz, C H 3), 0.97 (dtv, 6 H, 3Jhh «J * hp« 7.5 Hz, C H 3), 1,11 (dtv, 6 H, 3Jhh «J * hp« 7,8 Hz, C H 3), 1,42 (dtv, 6 H, 3Jhh «J * hp« 8.9 Hz, C H 3), 1.63 (s, 3H, C H ^ pz), 2.20 (m, 4H, CH), 2.87 (s, 3H, C H 3-3pz), 3.16 (m, 4H, C H 2), 6.34 (s, 1H, Car-4pz H ), 6.85 (t, 4H, 3Jhh = 7.2 Hz, pCa H ( BPh4)), 7.00 (t, 8H, 3Jhh = 7.4 Hz, mCaH (BPh4)), 7.06 (d, 2H, 3Jhh = 7.9 Hz, mCaH (PNP)), 7.33 ( s, a ,, 8H, oCarH (BPh4)), 7.56 (t, 3Jhh = 7.7 Hz, pCa H (PNP)).
    [0260] 13 C { 1 H} NMR (CD2Cl2, 25 ° C, 100 MHz): 5 12.7 (s, C H3-5 pz), 16.9 (s, C H3), 17.3 (s, C H3) , 17.9 (s, C H3), 18.3 (s, C H3-3pz), 18.7 (s, C H3), 23.5 (tv, J * cp = 12.1 Hz, C H ), 24.9 (tv, J * cp = 8.3 Hz, C H), 35.1 (tv, J * cp = 8.5 Hz, C H2), 115.6 (s, C ar-4pzH ), 121.9 (s, p C arH (BPh4)), 122.8 (s, m C arH (PNP)), 125.8 (s, m C arH (BPh4)), 135.8 (s, or C arH (BPh4)), 140.3 (s, p C arH (PNP)), 147.3 (s, C ar-pz), 152.1 (s, C ar-pz), 162.3 (t, 2JcP = 6.4 Hz, O C ar (PNP)), 163.9 (s, i C ar (BPh4)), 205.2 (s, C S2).
    [0261] Elemental Analysis (%): Calculated for C49H62BN3NiP2S2, C, 66.23; H, 7.03; N, 4.73; S, 7.22, Found: C, 66.26; H, 6.76; N, 4.75; S, 6.96.
    [0262]
    [0263] [(PCP) Ni-SC (O) Me 2 Pz], 10b . In a small Schlenk tube, about 20 mL in capacity, closed with a septum and magnetic stirrer, complex 4b (0.100 g, 0.20 mmol) is dissolved in the smallest amount of hexane possible (~ 5 mL). The septum is replaced by a new one (without drilling), the inert gas inlet is closed and cooled to -80 ° C. Complex 4b is poorly soluble at this temperature, and precipitates resulting in a yellow suspension. Another Schlenk tube of similar is prepared Characteristics, and the initial atmosphere of N2 is displaced with carbonyl sulfide gas (SCO) from a commercial gas bale. With a hermetic gas syringe with PTFE plunger, fitted with a gas valve, and a long thin needle (diameter 0.1 mm), 8 mL of SCO are taken at the ambient pressure and temperature (0.33 mmol ), and the valve closes. The septum of the Schlenk tube containing the solution of the reagent is then carefully drilled, making the needle reach to the bottom. While the contents are shaken, the valve of the syringe is opened and the gas is allowed to penetrate the tube (whose internal pressure has decreased on cooling), bubbling at a moderate rate. The needle is removed, the pore left with a little silicone grease is sealed, and the seal is secured with a piece of Parafilm®. The cooling bath is removed, allowing the mixture to reach room temperature, maintaining the agitation. The precipitate of 2b dissolves, and as it reacts with the SCO, its color changes to a more intense orange-reddish hue. When, when the ambient temperature is reached, the solution presents a homogenous appearance and without solids in suspension, the agitation is stopped and the mixture is allowed to stand undisturbed for 12 h. After a few minutes the formation of the first crystals of the product, in the shape of a needle, is gradually seen and gradually blocks of dark color are formed. At the end of the prescribed time, the tube is again connected to the line, the supernatant liquid is decanted and the crystals are dried by suction with a cannula topped on a paper filter. In no case should they be exposed to the vacuum because they lose SCO. Yield, 0.095 g, 0.17 mmol, 86%.
    [0264]
    [0265] 31 P {1 H} NMR (C6D6, 25 ° C, 160 MHz): 552.9 ppm.
    [0266] 1 H NMR (C6D6, 25 ° C, 400 MHz): 50.86 (dtv, 12H, 3Jhh «J * hp« 6.2 Hz, CH3), 0.99 (dtv, 12H, 3Jhh «J * hp« 7 , 0 Hz, CH3), 1.70 (s, 3H, CHwspz), 2.01 (s, a ,, 4H, CH), 2.62 (s, 3H, CH3-5pz), 2.83 (s) , a ,, 4H, CH2), 5.59 (s, 1H, Car-4pzH), 6.89 (d, 2H, 3Jhh = 7.1 Hz, mCaH), 7.01 (t, 1H, 3Jhh = 7, 1 Hz, pCarH).
    [0267] 13C {1 H} NMR (C6D6, 25 ° C, 100 MHz): 5 12.1 (s, CH3-5pz), 14.0 (s, CH3-3pz), 17.9 (s, CH3), 24, 2 (tv, J * cp = 8.9 Hz, CH), 34.7 (tv, J * cp = 11.6 Hz, CH2), 110.7 (s, Car-4pzH), 121.5 (tv , J * CP = 8.5 Hz, mCarH), 124.3 (s, pCarH), 142.0 (s, Car-3pz), 149.8 (tv, J * CP = 13.1 Hz, OCar), 150 , 1 (s, Car-5pz), 161.2 (t, 2Jcp = 17.9 Hz, / Car), 175.5 (s, COS).
    [0268]
    [0269] [(POCOP) Ni-SC (O) Me2Pz], 11b. This reaction has been studied by means of NMR spectroscopy, without trying to isolate the product. In an MRI tube, dissolve the complex 5b (0.020 g, 0.040 mmol) in CD2Cl2 (0.5 mL) and an orange solution is obtained. From a syringe bubbles COS (2 mL). The color of the solution intensifies, changing to a dark red tone. The change is completed in about 1 minute. The NMR spectra are then recorded, which indicate that the conversion is quantitative.
    [0270] 31 P {1 H} NMR (CD2Cl2, 25 ° C, 160 MHz): 5181.4 ppm.
    [0271] 1 H NMR (CD 2 Cl 2, 25 ° C, 400 MHz): 5 1.09 (dtv, 12 H, 3 Jhh «J * hp« 7.1 Hz, C H 3), 1.20 (dtv, 12 H, 3 Jhh « J * hp «8.1 Hz, C H 3), 1.78 (s 3 H, C H ^), 2.35 (m, 4 H, CH), 2.52 (s, 3 H, C H 3-pz ), 6.01 (s, 1H, Car-4pz H ), 6.37 (d, 2H, 3Jhh = 7.9 Hz, mCar H ), 6.88 (d, 1H, 3Jhh = 7.9 Hz, pCarH.
    [0272] 13 C {1 H} NMR (CD 2 Cl 2, 25 ° C, 100 MHz): 5 12.5 (s, C H 2 z), 13.8 (s, C H 2 z), 16.7 (s, C H 3) , 17.3 (s, C H3), 29.6 (tv, J * cp = 9.4 Hz, C H), 104.5 (tv, J * cp = 5.7 Hz, m C arH), 111.3 (s, C ar-4pzH), 126.9 (s, p C arH), 128.5 (tv, J * CP = 22.2 Hz, O C ar), 142.7 (s, C ar-pz), 151.5 (s, C ar-pz), 166.7 (t, 2 Jcp = 10.1 Hz, / C ar), 175.9 (s, C OS).
    [0273]
    [0274] [(PNP) Ni-SC (O) Me2Pz] + [BPh4] ', 12b . This reaction has been studied by means of NMR spectroscopy, without trying to isolate the product. In an NMR tube, complex 6b (0.02 g, 0.025 mmol) is dissolved in CD2Cl2 (0.5 mL), and 2 mL of SCO is bubbled from a gas syringe. There is an instantaneous change of color to dark burgundy. The NMR spectra are then recorded, which indicate that the conversion is quantitative.
    [0275] 31 P {1 H} NMR (CD2Cl2, 25 ° C, 160 MHz): 535.8 ppm.
    [0276] 1 H NMR (CD 2 Cl 2, 25 ° C, 400 MHz): 51.08 (m, 24H, C H 3), 1.62 (s, 3 H, C H 3-pz), 2.25 (m, 4H, C H ), 2.56 (s, 3H, C H 3-pz), 3.16 (s, a ,, 4H, C H 2), 6.22 (s, 1H, Car-4pz H ), 6, 86 (t, 4H, 3Jhh = 7.0 Hz, pCar H (BPh4)), 7.01 (t, 8 H, 3 Jhh = 7.3 Hz, mCarH (BPh4)), 7.08 (d, 2H, 3 Jhh = 7.9 Hz, mCar H (PNP)), 7.34 (s, a, 8 H, oCar H (BPh4)), 7.56 (t, 1H, 3Jhh = 7.8 Hz, pCar H (PNP)).
    [0277]
    [0278] Example 6. Study of the reversibility of the reactions with CS2 and COS
    [0279]
    [0280] The stability of the neutral complexes [(PCP) Ni-SC (S) Me2Pz] ( 7b ) and [(PCP) Ni-SC (O) Me2Pz] ( 10b ) was investigated qualitatively. Solid samples weighing approximately 5mg were kept under vacuum for 8h at room temperature or 60 ° C, and after this time they were analyzed by recording their 31P {1H} spectra in solution. Complex 10b completely reverses precursor 4b at temperature ambient.
    [0281]
    [0282] Example 7. Determination of the equilibrium constant and thermodynamic parameters for the reaction of the compounds of the invention with CS2
    [0283]
    [0284] A 0.013 M solution of 7b in deuterated toluene is prepared, and 0.6 mL of it is placed in an NMR tube fitted with a Young key. The NMR spectra are recorded to check the purity of the sample. In preliminary experiments, it was determined that the complex dissociates into 4b and CS2 when heated at 125 ° C, but recovers when it remains at room temperature. The process is very selective, and can be repeated as many times as necessary without the sample decomposing appreciably. Then, the definitive experiments are carried out, for which the sample is placed in a bath at 125 ° C for 10 - 15 min., And then it is taken to the spectrometer probe, previously stabilized at the temperature of the experiment (75, 50 or 25 ° C), recording its spectrum of 31P {1H} at regular intervals, until it is considered that the situation of chemical equilibrium has been reached. Once the initial concentration of the complex 7b is known , and assuming that the concentration of CS2 is necessarily the same as that of 4b , the ratio of the intensities of the 31P signals allows the constant equilibrium value (Keq) to be calculated. On the other hand, the Keq values at the mentioned temperatures allow to calculate the thermodynamic parameters of the reaction (AH °, AS ° and AG °). These data allow to estimate the composition of the equilibrium at any given temperature.
    [0285]
    [0286]
    [0287]
    [0288]
    [0289] Thermodynamic data for the reaction of 2b with CS2: AH ° = 11.2 (7) Kcalmol-1; AS ° = -17 (2) Cal mol-1K-1; AG ° (298 K): -6.25 (12) Kcal mol-1.
    [0290] Example 8. Color changes associated with the reactions of the complexes with CS two .
    [0291]
    [0292] The reactions of complexes 4b , 5b or 6b with CS2 or COS are accompanied by very evident color changes. Figure 2 shows a qualitative assay illustrating such changes. Solutions of 0.05 M concentration of 4b (Left), 5b (center) and 6b (right) in dichloromethane (0.6 mL) were treated with 5. ^ L of CS2, which is equivalent to a concentration of 0.15 M. Figure 2 shows the color evolution after 1 min, 4 min and 1 h, after which it can be assured that the reaction has been completed. These images allow to appreciate that the speed of the reactions decreases in the order 4b > 6b > 5b . However, the most marked color change seems to occur with 6b .
    [0293]
    [0294] In order to quantify the intensity of the color change, the UV-Vis spectra of 4b and 6b have been recorded , as well as those of their adducts with CS2 ( 7b and 8b , respectively) in CH2Cl2 (concentration 10-4 M; of complexes 7b and 8b were recorded in a mixture of CH2Cl2 and 10% CS2 V: V, corresponding to [CS2] = 1.67 M to ensure that the spectrum corresponds to a single chemical species). Figure 3 shows the normalized spectra (the ordinate scale corresponds to the molar absorption coefficient) of the derivatives containing PCP and POCOP ligands in the region between 350 and 700 nm (near and visible UV). Both the initial and final products have absorption maxima at approximately 400 nm. The increase in color intensity is reflected in the considerable increase in the absorption bands of products with CS2. This increase is best seen in the lower part of the figure, in which the difference spectra are represented (As = sproduct Cs2 - sreactive). The maximum increase is located at 424 nm (As = 7500 L mo lcm -1) for the pair 4b / 6b or 408 nm (As = 9200 L mo lcm -1) for 7b / 8b . The higher intensity of the maximum in the latter case confirms the qualitative visual assessment that the color change is more intense for the complex with POCOP ligand.
    权利要求:
    Claims (26)
    [1]
    1. Compound of formula (I)

    [2]
    2. Compound according to claim 1, wherein M is selected from Ni (II) and Pd (II).
    [3]
    3. Compound according to any one of the preceding claims, wherein M is Ni (II).
    [4]
    4. Compound according to any of the preceding claims, wherein X is selected from O and CH2.
    [5]
    5. Compound according to any one of the preceding claims, wherein X is CH2.
    [6]
    6. Compound according to any of the preceding claims, wherein Y is P (iPr) 2.
    [7]
    Compound according to any one of the preceding claims, wherein L is selected from 3-methylpyrazole, 3,5-dimethylpyrazole, imidazole, 2-methylimidazole, 4-methylimidazole, and 1,2,4-triazole.
    [8]
    8. Compound according to any one of the preceding claims, wherein L is 3,5-dimethylpyrazole.
    [9]
    9. Compound according to claim 1, of formula (la)

    [10]
    10. Compound according to claim 9, wherein M is selected from Ni (II) and Pd (II).
    [11]
    11. Compound according to any of claims 9 to 10, wherein M is Ni (II).
    [12]
    12. Compound according to any of claims 9 to 11, wherein X is selected from O and CH2.
    [13]
    13. Compound according to any of claims 9 to 12, wherein X is CH2.
    [14]
    14. Compound according to any of claims 9 to 13, wherein Y is P (iPr) 2.
    [15]
    15. The compound according to any of claims 9 to 14, wherein L is selected from 3-methylpyrazole, 3,5-dimethylpyrazole, imidazole, 2-methylimidazole, 4-methylimidazole, and 1,2,4-triazole.
    [16]
    16. Compound according to any of claims 9 to 15, wherein L is 3,5-dimethylpyrazole.
    [17]
    17. Compound according to claim 1, of formula (Ib)

    [18]
    18. Compound according to claim 17, wherein M is selected from Ni (II) and Pd (II).
    [19]
    19. Compound according to any of claims 17 to 18, wherein M is Ni (II).
    [20]
    20. Compound according to any of claims 17 to 19, wherein X is selected from O and CH2.
    [21]
    21. Compound according to any of claims 17 to 20, wherein X is CH2.
    [22]
    22. Compound according to any of claims 17 to 21, wherein Y is P (iPr) 2.
    [23]
    23. The compound according to any of claims 17 to 22, wherein L is selected from 3-methylpyrazole, 3,5-dimethylpyrazole, imidazole, 2-methylimidazole, 4-methylimidazole, and 1,2,4-triazole.
    [24]
    24. Compound according to any of claims 17 to 23, wherein L is 3,5-dimethylpyrazole.
    [25]
    25. Use of the compound of general formula (I), as defined in claims 1 to 24, for the fixation and / or detection of CS2.
    [26]
    26. Device for the fixation and / or detection of CS2, comprising at least one compound of general formula (I) as defined in claims 1 to 24.
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    ES2710793B2|2020-03-19|
    WO2019081796A3|2019-06-20|
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