Method of preparing metal complexes of formula Z-M, in particular carbene-metal complexes
20210198286 · 2021-07-01
Assignee
Inventors
Cpc classification
B01J2231/4211
PERFORMING OPERATIONS; TRANSPORTING
B01J31/2273
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
The present invention relates to an improved method of preparing metal complexes, in particular carbene-metal complexes. The method comprises the step of subjecting a salt of formula Z.sup.+—X.sup.− and a non-ionic metal salt of formula ML.sub.n or subjecting a metallate of formula Z.sup.+ . . . ML.sub.nX.sup.− to a mechanical mixing process in the presence of a base. The method allows to formation of heterocyclic carbene metal complexes such as a nitrogen-containing heterocyclic carbene (NHC)-metal complexes. The invention also relates to the use of metal complexes, in particular carbene-metal complexes such as heterocyclic carbene-metal complexes obtainable by the method according to the present invention as catalysts.
Claims
1. A method of preparing a metal complex of formula Z-M, the method comprising the steps of i1) providing a salt of formula Z.sup.+—X.sup.− and a non-ionic metal salt of formula ML.sub.n; or i2) providing a metallate of formula Z.sup.+. . . ML.sub.nX.sup.−, with Z comprising a two-electron donor ligand; X comprising an anion; M comprising a metal; L comprising an anion or an electron donor ligand; and ii) subjecting the salt of formula Z.sup.+—X.sup.− and the metal salt of formula ML of step i1) or the metallate of formula Z.sup.+. . . ML.sub.nX.sup.−, of step i2) to a mechanical mixing process in the presence of a base to form said metal complex of formula Z-M.
2. The method according to claim 1, wherein said method does not require the use of a solvent.
3. The method according to claim 1, wherein said salt of formula Z.sup.+—X.sup.− of step i1) has a single two-electron donor ligand Z or wherein said metallate of formula Z.sup.+. . . ML.sub.nX.sup.− of step i2) has a single two-electron donor ligand Z.
4. The method according to claim 1, wherein said non-ionic metal salt of formula ML comprises a single metal M.
5. The method according to claim 1, wherein said metal complex of formula Z-M has a single two-electron donor ligand Z.
6. The method according to claim 1, wherein Z comprises a carbene, a phosphorus donor ligand, a nitrogen donor ligand or any other heteroatom donor ligand.
7. The method according to claim 1, wherein said metal complex of formula Z-M comprises a carbene-metal complex.
8. The method according to claim 7, wherein the nitrogen-containing heterocyclic carbene ligand is in the form of ##STR00027## wherein each of the groups R may be the same or different, the groups R.sup.1 where present may be the same or different and the dashed line in the ring represents optional unsaturation, when R.sup.1 and R.sup.2 are absent; wherein each R and R.sup.1 is independently for each occurrence selected from: hydrogen, a primary, secondary or tertiary alkyl group that may be unsaturated and may be substituted or unsubstituted and may be cyclic, substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or a functional group selected from the group consisting of halide, hydroxyl, alkoxyl, aryloxyl, sulfhydryl, cyano, cyanate, thicyanato, amino, nitro, nitroso, sulfo, sulfonato, boryl, borono, phosphono, phosphonato, phosphinato, phospho, phosphino and silxy; and wherein one or more of the carbon atoms in the ring apart from the carbene carbon may be substituted with B, O, P or S.
9. The method according to claim 7, wherein the nitrogen-containing heterocyclic carbene ligand is of the form ##STR00028## wherein each of the groups R, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be the same or different and the dashed line in the ring represents optional unsaturation, when R1 and R2 are absent; and wherein R and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently for each occurrence selected from: hydrogen, a primary, secondary or tertiary alkyl group that may be unsaturated and may be substituted or unsubstituted and may be cyclic, substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or a functional group selected from the group consisting of halide, hydroxyl, alkoxyl, aryloxyl, sulfhydryl, cyano, cyanate, thicyanato, amino, nitro, nitroso, sulfo, sulfonate, boryl, borono, phosphona, phosphonato, phosphinato, phospho, phosphino and siloxy.
10. The method according to claim 7, wherein the nitrogen-containing heterocyclic ligand Z is selected from the group consisting of ##STR00029##
11. The method according to claim 1, wherein X is selected from the group consisting of halides, carboxylates, alkoxy groups, aryloxy groups, alkylsulfonates, acetates, trifluoroacetates, tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates, cyanides, thiocyanates, isothiocyanates, cyanates, isocyanates, azides and selenocyanates.
12. The method according to claim 1, wherein M comprises a transition metal and/or wherein L is selected from the group consisting of fluoride (F.sup.−), chloride (Cl.sup.−), bromide (Br.sup.−), iodide (I.sup.−), triflate (trifluoromethane sulfonate) (OTf.sup.−), acetate (OAc.sup.−), trifluoroacetate (TFA.sup.−), tetrafluoroborate (BF.sub.4.sup.−), hexafluorophosphate (PF.sub.6.sup.−), hexafluoroantimonate (SbF.sub.6.sup.−), sulfate (SO.sub.4.sup.2−) and phosphate (PO.sub.3.sup.2−).
13. The method according to claim 1, wherein said mechanical mixing process comprises ball milling, hand grinding, twin-screw extrusion or a combination thereof.
14. The method according to claim 1, wherein said base is selected from the group consisting of carbonates, hydrogen carbonates, phosphates and amines.
15. The method according to claim 1, wherein said metallate of step i2) is obtainable from mixing a salt of formula Z.sup.+—X.sup.− with a metal salt of formula ML while subjecting to a mechanical mixing process.
16. A carbene metal complex obtainable from the method of claim 1 and suitable for use as a catalyst.
17. The method according to claim 7, wherein said carbene-metal complex comprises a nitrogen-containing heterocyclic carbene (NHC) ligand.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0072] The present invention will be discussed in more detail below, with reference to the attached drawings, in which:
[0073]
[0074]
DESCRIPTION OF EMBODIMENTS
[0075] The present invention will be described with respect to particular embodiments and with reference to certain drawings but the invention is not limited thereto but only by the claims.
[0076] All reactions were carried out in a planetary mill.
[0077] The following abbreviations are used in the examples [0078] IPr.HCl: 1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-3-ium chloride [0079] SIPr.HCl: 1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-3-ium chloride [0080] IMes.HCl: 1,3-dimesityl-1H-imidazol-3-ium chloride [0081] SIMes.HCl: 1,3-dimesityl-4,5-dihydro-1H-imidazol-3-ium chloride [0082] IPr*.HCl: 1,3-bis(2,6-dibenzhydryl-4-methylphenyl)-1H-imidazol-3-ium chloride [0083] IAd.HCl: 1,3-di((3S,5S,7S)-adamantan-1-yl)-1H-imidazol-3-ium chloride [0084] ICy.HCl: 1,3-dicyclohexyl-1H-imidazol-3-ium chloride [0085] ItBu.HCl: 1,3-di-tert-butyl-1H-imidazol-3-ium chloride [0086] MIC A.HCl: 4-(4-(tert-butyl)phenyl)-1-(2,6-diisopropylphenyl)-3-methyl-1H-1,2,3-triazol-3-ium chloride MIC B.HCl: 1-benzyl-4-(4-(tert-butyl)phenyl)-3-methyl-1H-1,2,3-triazol-3-ium chloride [0087] CAAC.sup.Me2.HCl: 1-(2,6-diisopropylphenyl)-2,2,4,4-tetramethyl-3,4-dihydro-2H-pyrrol-1-ium chloride [0088] CAAC.sup.Cy.HCl: 2-(2,6-diisopropylphenyl)-3,3-dimethyl-2-azaspiro[4.5]dec-1-en-2-ium chloride:
[0089] The chemical structure of a number of the above mentioned N-heterocyclic carbene ligand salts are shown in
Example 1: Synthesis of [IPrH][CuCl.SUB.2.] Metallate
[0090] A milling jar was charged with IPrHCl (4 g), CuCl and milling balls. The jar was placed in the planetary mill. The mixture was ground by ball milling.
##STR00011##
[0091] In a vial a powder was recovered from the bowl. A .sup.1H NMR spectrum was recorded to confirm product formation. The .sup.1H NMR spectrum is given in
[0092] A microcrystalline solid product was isolated. The .sup.1H NMR spectrum of the product is given in
[0093] The total yield of the obtained powder is 97%.
[0094] The analyses of the .sup.1H NMR spectra of
Example 2: Synthesis of [SIPrH][CuCl.SUB.2.] Metallate
[0095] SIPr.HCl (2 g) and CuCl were ground by ball milling.
##STR00012##
[0096] The powder was recovered from the reactor. The .sup.1H NMR spectrum of the powder is given in
[0097] The solid content in the marbles as well as the remaining solid present in the reactor and on the lid was recovered. The .sup.1H NMR spectrum is given in
[0098] The total yield of the obtained powder is 97%.
[0099] The analyses of the .sup.1H NMR spectra of
[0100] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 8.11 (s, H.sub.NCHN, 1H), 7.45 (t, p-H.sub.Ar, 2H), 7.24 (d, m-H.sub.Ar, 4H), 4.68 (s, H.sub.CH—CH, 4H), 2.98 (m, CH(iPr), 4H), 1.37 (d, (CH.sub.3).sub.2, 12H), 1.21 (d, (CH.sub.3).sub.2, 12H) (
Example 3: Synthesis of [IPrH][CuCl.SUB.3.] Metallate
[0101] IPrHCl and CuCl.sub.2 were ground by ball milling.
##STR00013##
[0102] The powder was recovered from the reactor. The .sup.1H NMR spectrum of the powder is given in
[0103] The solid content in the marbles as well as the remaining solid present in the reactor and on the lid was recovered. The .sup.1H NMR spectrum is given in
[0104] The product was obtained as powder in 99% yield.
[0105] The analyses of the .sup.1H NMR spectra of
[0106] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 7.84 (m, p-H.sub.Ar, 2H), 7.57 (m, m-H.sub.Ar, 4H), 7.12 (m, H.sub.NCHN, 1H), 2.67 (m, CH(iPr), 4H), 1.81 (m, (CH.sub.3).sub.2, 12H), 1.71 (m, (CH.sub.3).sub.2, 12H) (
Example 4: Synthesis of [IPrH][PdCl.SUB.3.] Metallate
[0107] [IPrH][PdCl.sub.3] metallate was synthesized on a small scale (example 4a) and on a large scale (example 4b).
Example 4a: Small Scale Synthesis of [IPrH][PdCl.SUB.3.] Metallate
[0108] IPr.HCl (0.5 g) and PdCl.sub.2 were ground by ball milling.
##STR00014##
[0109] 133 mg powder was recovered from the reactor. A further 0.5 g of product was isolated.
[0110] The total yield of the obtained powder is 97% yield.
Example 4b: Large Scale Synthesis of [IPrH][PdCl.SUB.3.] Metallate
[0111] IPr.HCl (1 g) and PdCl.sub.2 were ground using ball milling.
[0112] The product was obtained as powder in 99% (1.4 g) yield. The .sup.1H NMR spectrum is given in
[0113] The analysis of the .sup.1H NMR spectrum of
[0114] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 9.22 (s, H.sub.NCHN, 1H), 8.40 (s, H.sub.CH═CH, 2H), 7.59 (t, p-H.sub.Ar, 2H), 7.35 (d, m-H.sub.Ar, 4H), 2.54 (m, CH(iPr), 4H), 1.32 (d, (CH.sub.3).sub.2, 12H), 1.22 (d, (CH.sub.3).sub.2, 12H).
Example 5: Synthesis of [Pd(IPr)(η.SUP.3.-cin)Cl] Complex
[0115] A milling jar was charged with [IPrH][Pd(η.sup.3-cin)Cl.sub.2], K.sub.2CO.sub.3 and milling balls. The mixture was ground by ball milling.
##STR00015##
[0116] A .sup.1H NMR spectrum was recorded to confirm the obtained complex.
[0117] The powder content from the lid, the reactor bowl and the balls was recovered. The solid was washed.
[0118] The product was obtained as powder in 87% yield. The .sup.1H NMR spectrum is given in
[0119] The analysis of the .sup.1H NMR spectrum of
[0120] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 7.48 (t, H.sub.CH═CH, 2H), 7.30 (d, m-H.sub.Ar, 4H), 7.16 (d, H.sub.Ar, 7H), 5.12 (m, H.sub.cin, 1H), 4.35 (d, H.sub.cin 1H), 2.94 (m, CH(iPr), 4H), 1.76 (d, H.sub.cin, 1H), 1.40 (d, (CH.sub.3).sub.2, 12H), 1.14 (d, (CH.sub.3).sub.2, 12H).
Example 6: Synthesis of [Pd(IPr)(η.SUP.3.-cin)Cl] Complex
[0121] [IPrH][Pd(η.sup.3-cin)Cl.sub.2] and K.sub.2CO.sub.3 were ground by ball milling.
##STR00016##
[0122] A .sup.1H NMR was recorded to confirm product formation.
[0123] The powder content on the lid, from the reactor bowl and the balls was recovered.
[0124] The product was obtained as a microcrystalline powder in 93% yield. The .sup.1H NMR spectrum is given in
[0125] The analysis of the .sup.1H NMR spectrum of
[0126] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 7.48 (t, H.sub.CH═CH, 2H), 7.30 (d, m-H.sub.Ar, 4H), 7.16 (d, H.sub.Ar, 7H), 5.12 (m, H.sub.cin, 1H), 4.35 (d, H.sub.cin 1H), 2.94 (m, CH(iPr), 4H), 1.76 (d, H.sub.cin, 1H), 1.40 (d, (CH.sub.3).sub.2, 12H), 1.14 (d, (CH.sub.3).sub.2, 12H).
Example 7: Synthesis of [Pd(SIPr)(η.SUP.3.-Cin)Cl] Complex
[0127] A milling jar was charged with SIPr.HCl, [Pd(η.sup.3-cin)(μ-Cl)].sub.2 and milling balls. The jar was then placed in a planetary mill. The mixture was ground by ball milling.
##STR00017##
[0128] A .sup.1H NMR spectrum was recorded which confirmed palladate formation (
[0129] Then, K.sub.2CO.sub.3 was added to the reactor and the reaction mixture was ground by ball milling. A .sup.1H NMR spectrum recorded on a sample after this procedure confirmed product formation.
[0130] The product was obtained as a microcrystalline powder in 89% yield. The .sup.1H NMR spectrum is given in
[0131] The analyses of the .sup.1H NMR spectrum of
[0132] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 7.88 (s, H.sub.NCHN, 1H), 7.50 (m, p-H.sub.Ar, 4H), 7.24 (m, H.sub.Ar, 8H), 5.2 (s, H.sub.cin, 1H), 4.93 (S, N.sub.CH—CH, 4H), 4.51 (d, H.sub.cin, 1H), 3.93 (m, CH(iPr), 4H), 3.04 (s, H.sub.cin, 1H), 1.41 (m, CH.sub.3).sub.2, 12H), 1.24 (d, CH.sub.3).sub.2, 12H) (
[0133] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 7.38 (t, p-H.sub.Ar, 2H), 7.24 (d, m-H.sub.Ar, 4H), 7.1 (s, HPh, 5H), 5.09 (m, H.sub.cin, 1H), 4.33 (d, H.sub.cin, 1H), 4.02 (S, H.sub.CH═CH, 4H), 3.43 (m, CH(iPr), 4H), 2.88 (s, H.sub.cin, 1H), 1.42 (m, CH.sub.3).sub.2, 12H), 1.27 (d, CH.sub.3).sub.2, 12H) (
Example 8: Synthesis of Cu(IPr)Cl Complex
[0134] [IPrH][CuCl.sub.2] and K.sub.2CO.sub.3 were ground using ball milling.
##STR00018##
[0135] The product was obtained as a powder in 88% (163.2 mg) yield. The .sup.1H NMR spectrum is given in
[0136] The analysis of the .sup.1H NMR spectrum of
[0137] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 7.52 (m, H.sub.CH═CH, 2H), 7.31 (d, m-H.sub.Ar, 4H), 7.14 (t, p-H.sub.Ar, 2H), 2.61 (m, CH(iPr), 4H), 1.31 (d, (CH.sub.3).sub.2, 12H), 1.24 (d, (CH.sub.3).sub.2, 12H).
Example 9: Synthesis of Cu(SIMes)Cl Complex
[0138] SIMes.HCl and CuCl were ground using ball milling.
##STR00019##
[0139] A .sup.1H NMR spectrum was recorded to confirm formation of the cuprate.
[0140] K.sub.2CO.sub.3 was added to the reaction and then ground by ball milling. A .sup.1H NMR spectrum confirmed product formation (
[0141] The product was obtained as a microcrystalline powder in 87% yield. The .sup.1H NMR spectrum is shown in
[0142] The analyses of the .sup.1H NMR spectra of
[0143] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 8.48 (s, H.sub.NCHN, 1H), 7.02 (s, H.sub.Ar, 4H), 4.61 (s, H.sub.CH—CH, 4H), 2.41 (s, o-CH.sub.3, 12H), 2.33 (s, p-CH.sub.3, 6H).
[0144] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 6.88 (s, H.sub.Ar, 4H), 3.89 (s, N.sub.CH—CH, 4H), 2.25 (s, o-CH.sub.3, 12H), 2.23 (s, p-CH.sub.3, 6H).
Example 10: Synthesis of [Pd(IPr)(allyl)Cl]
[0145] IPr.HCl and [Pd(allyl)Cl] dimer were ground using ball milling.
##STR00020##
[0146] A .sup.1H NMR spectrum confirmed palladate formation (
[0147] K.sub.2CO.sub.3 was added and then mixed by ball milling.
[0148] The product was obtained as a microcrystalline powder in 93% yield. The .sup.1H NMR spectrum is given in
[0149] The analyses of the .sup.1H NMR spectrum of
[0150] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 9.23 (s, H.sub.NCHN, 1H), 8.34 (d, H.sub.CH═CH, 2H), 7.57 (d, p-H.sub.Ar, 2H), 7.36 (d, m-H.sub.Ar, 4H), 5.28 (s, H.sub.allyl, 1H), 3.91 (s, H.sub.allyl, 2H), 2.83 (s, H.sub.allyl, 2H), 2.50 (m, CH(iPr), 4H), 1.32 (m, CH.sub.3).sub.2, 12H), 1.24 (d, CH.sub.3).sub.2, 12H).
[0151] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 7.44 (t, p-H.sub.Ar, 2H), 7.28 (d, m-H.sub.Ar, 4H), 7.15 (s, H.sub.CH═CH, 2H), 4.80 (m, H.sub.allyl, 1H), 3.90 (dd, H.sub.allyl, 1H), 3.15 (m, CH(iPr), 2H), 3.05 (d, H.sub.allyl, 1H), 2.87 (m, CH(iPr), 2H), 2.79 (d, H.sub.allyl, 1H), 1.59 (s, H.sub.allyl, 1H), 1.30 (dd, CH.sub.3).sub.2, 12H), 1.10 (dd, CH.sub.3).sub.2, 12H).
Example 11: Synthesis of [IPr.H][CuCl.SUB.2.] Metallate
[0152] A milling jar was charged with: IPrHCl, CuCl and milling balls. The mixture was ground. The product was obtained in 97% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.27 (d, 12H), 1.33 (d, 13H), 2.43 (spt, 4H), 7.40 (d, 4H), 7.60-7.67 (m, 2H), 7.84 (s, 2H), 9.21 (s, 1H).
Example 12: Synthesis of [Cu(Cl)(IPr)] Complex
[0153] A milling jar was charged with: IPrHCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 78% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.24 (d, 12H) 1.31 (d, 12H), 2.58 (spt, 4H), 7.14 (s, 2H), 7.31 (d, 4H), 7.47-7.53 (m, 2H).
Example 13: Synthesis of [SIPr.H][CuCl.SUB.2.] Metallate
[0154] A milling jar was charged with: SIPr.HCl, CuCl and milling balls. The mixture was ground. The product was obtained in 96% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.28 (d, 12H), 1.44 (d, 12H), 2.97-3.12 (spt, 4H), 4.73 (s, 4H), 7.31 (d, 4H), 7.46-7.55 (m, 2H), 8.15 (s, 1H).
Example 14: Synthesis of [Cu(Cl)(SIPr)] Complex
[0155] A milling jar was charged with: SIPr.HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 66% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.36 (d, 12H) 1.38 (d, 12H) 3.08 (spt, 4H) 4.03 (s, 4H) 7.25 (d, 4H) 7.37-7.45 (m, 2H).
Example 15: Synthesis of [IMes.H][CuCl.SUB.2.] Metallate
[0156] A milling jar was charged with: IMes.HCl, CuCl and milling balls. The mixture was ground. The product was obtained in 98% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 2.18 (s, 12H), 2.39 (s, 6H), 7.10 (s, 4H), 7.64 (s 2H), 9.25 (s, 1H).
Example 16: Synthesis of [Cu(Cl)(IMes)] Complex
[0157] A milling jar was charged with: IMes.HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 65% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 2.11 (s, 12H) 2.36 (s, 6H) 7.01 (s, 4H) 7.06 (s, 2H).
Example 17: Synthesis of [SIMes.H][CuCl.SUB.2.] Metallate
[0158] A milling jar was charged with: SIMes.HCl, CuCl and milling balls. The mixture was ground. The product was obtained in 92% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 2.32 (s, 6H), 2.40 (s, 12H), 4.59 (br s, 4H), 7.01 (s, 4H), 8.36 (s, 1H).
Example 18: Synthesis of [Cu(Cl)(SIMes)] Complex
[0159] A milling jar was charged with: SIMes.HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 65% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 2.31 (s, 6H) 2.32-2.34 (m, 1H) 2.32 (s, 11H) 3.96 (s, 4H) 6.96 (s, 4H).
Example 19: Synthesis of [Cu(Cl)(IPr*)] Complex
[0160] A milling jar was charged with: IPr*HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 72% yield.
Example 20: Synthesis of [Cu(Cl)(ItBu)] Complex
[0161] A milling jar was charged with: ItBu.HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 48% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.79 (s, 18H), 7.05 (s, 2H).
Example 21: Synthesis of [Ag(Cl)(IPr)] Complex
[0162] A milling jar was charged with: IPrHCl, AgCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 70% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.23 (d, 12H) 1.29 (d, 12H) 2.55 (spt, 4H) 7.22 (d, 2H) 7.31 (d, 4H) 7.48-7.54 (m, 12H).
Example 22: Synthesis of [Ag(Cl)(SIPr)] Complex
[0163] A milling jar was charged with: SIPr.HCl, AgCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 70% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.35 (d, 12H) 1.37 (d, 12H) 3.07 (spt, 4H) 4.08 (s, 4H) 7.24-7.29 (m, 4H) 7.39-7.45 (m, 2H).
Example 23: Synthesis of [Ag(Cl)(IPr*)] Complex
[0164] A milling jar was charged with: IPr*HCl, AgCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 64% yield.
Example 24: Synthesis of [Ag(Cl)(ICy)] Complex
[0165] A milling jar was charged with: ICy.HCl, AgCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product was obtained in 17% yield.
Example 25: Synthesis of [Rh(cod)(Cl)(IMes)] Metallate
[0166] A milling jar was charged with: IMes.HCl, [Rh(cod)(μ-Cl)]2, K.sub.2CO.sub.3 and milling balls. The mixture was ground. The product was obtained in 74% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.56 (br d, 4H) 1.71-1.94 (m, 4H) 2.12 (s, 6H) 2.40 (s, 64H) 2.41 (s, 6H) 3.31 (br d, 2H) 4.54 (br s, 2H) 6.96 (s, 2H) 7.02 (br s, 2H) 7.07 (br s, 2H).
Example 26: Synthesis of [Ir(cod)(Cl)(IMes)] Complex
[0167] A milling jar was charged with: IMes.HCl, [Rh(cod)(μ-Cl)].sub.2, K.sub.2CO.sub.3 and milling balls. The mixture was ground. The product was obtained in 94% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 1.17-1.39 (m, 4H) 1.52-1.80 (m, 4H) 2.17 (m, 6H) 2.36 (s, 6H) 2.37 (br s, 6H) 2.95-2.99 (m, 2H) 4.11-4.19 (m, 2H) 6.96 (br s, 2H) 6.98 (br s, 2H) 7.01 (br s, 2H).
Example 27: Synthesis of [Ag(Cl)(IAd)] Complex
[0168] A milling jar was charged with: IAd.HCl, AgCl and milling balls. The resulting solid mixture was ground and K.sub.2003 was added. The solids were further ground. The product was obtained in 48% yield.
Example 28: Synthesis of [Cu(Cl)(IAd)] Complex
[0169] A milling jar was charged with: IAd.HCl, CuCl and milling balls. To the resulting solid mixture K.sub.2CO.sub.3 was added. The solid mixture was further ground. The product was obtained in 20% yield.
Example 29: Synthesis of [Cu(Cl)(MIC A)] Complex
[0170] A milling jar was charged with: MIC A.HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product with the following structure was obtained in 58% yield:
##STR00021##
Example 30: Synthesis of [Cu(Cl)(CAAC.SUP.Me2.)] Complex
[0171] A milling jar was charged with: CAAC.sup.Me2.HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product with the following structure was obtained in 23% yield:
##STR00022##
Example 31: Synthesis of [Cu(Cl)(CAAC.SUP.Cy.)] Complex
[0172] A milling jar was charged with: CAAC.sup.Cy.HCl, CuCl and milling balls. The resulting solid mixture was ground and K.sub.2CO.sub.3 was added. The solids were further ground. The product with the following structure was obtained in 26% yield:
##STR00023##
Example 32: Synthesis of [Rh(cod)(Cl)(CAAC.SUP.Cy.)] Complex
[0173] A milling jar was charged with: CAAC.sup.Cy.HCl (100 mg), [Rh(cod)(μ-Cl)]2, K.sub.2CO.sub.3 and milling balls. The mixture was ground. The product with the following structure was obtained in 19% yield:
##STR00024##
Example 33: Synthesis of [Rh(cod)(Cl)(CAAC.SUP.Me2.)] Complex
[0174] A milling jar was charged with: CAAC.sup.Me2.HCl (100 mg), [Rh(cod)(μ-Cl)]2, K.sub.2CO.sub.3 and milling balls. The mixture was ground. The product with the following structure was obtained in 22% yield:
##STR00025##
Example 34: Catalysis: Suzuki-Miyaura Cross-Coupling: Synthesis of 4-Acetylbiphenyl
[0175] K.sub.2CO.sub.3 (207.3 mg, 1.5 mmol, 1.5 equiv.) and [Pd(IPr)(Cin)Cl] (12.9 mg, 0.02 mmol, 0.02 equiv.) were ground together by ball milling. Phenylboronic acid (199 mg, 1 mmol, 1 equiv.) and 4-bromoacetophenone (146.3 mg, 1.2 mmol, 1.2 equiv.) were added to the reaction mixture that was ground for 10 minutes.
##STR00026##
[0176] A .sup.1H NMR spectrum was recorded in order to confirm product formation. To obtain 4-acetylbiphenyl two additional 10-minute cycles were required.
[0177] Using a flask (250 mL), the powder content from the lid, the reactor bowl and from the balls was transferred using dichloromethane (approximately 25 mL). After filtration through Celite and washing of the Celite pad with 15 mL of dichloromethane, the dichloromethane solution was washed with brine (2×20 mL) and the organic phase was separated and dried over MgSO.sub.4. The solution was filtered through a paper filter and the volatiles were removed using a rotary evaporator then the solids placed under vacuum using a Schlenk vacuum line to remove any residual solvent overnight.
[0178] The product was obtained as powder in an 86% (168.6 mg) yield. The .sup.1H NMR spectrum is given in
[0179] The analysis of the .sup.1H NMR spectrum of
[0180] .sup.1H NMR (400 MHz, CDCl.sub.3) δ (ppm) 8.05 (d, H.sub.Ar, 2H), 7.7 (d, H.sub.Ar, 2H), 7.49 (m, H.sub.Ar, 2H), 2.64 (s, CH.sub.3, 3H).
[0181] Test results showed that synthesis of the catalyst and the use of the catalyst can be carried out in the same reactor using the same conditions. This means that the method according to the present invention allows to perform three steps without purification: [0182] 1) The metallate formation; [0183] 2) The carbene-metal complex formation, in particular nitrogen-containing heterocyclic carbene-metal complex formation; and [0184] 3) The use of the NHC-complex in a catalytic reaction.
[0185] Steps 1 and step 2 can be performed either in two steps or in a single step.