PROCESS FOR PREPARING HYDROSILANS FROM (PSEUDO-)HALO-SILANES BY ELECTROCHEMICAL MEANS

Abstract

The present invention relates to a process for preparing hydrosilanes by electrochemical reduction of corresponding (pseudo-)halosilanes in the presence of a transition metal complex as a hydride transfer agent, and a protonated (or deuterated) organic base as a proton (or deuterium) source. The process of the invention contributes to the circularity of the silicon element by enabling the recycling of (pseudo-)halosilane compounds, common waste products of silicon chemistry, into higher value-added hydrosilanes. Figure for the abstract: None

Description

Title of the invention: METHOD FOR PREPARING HYDROSILANS FROM (PSEUDO-)HALO-SILANES BY ELECTROCHEMICAL MEANS Technical field of the invention

[0001] The present invention is in the field of silane chemistry and more particularly in the synthesis of hydrosilane compounds having one to four Si-H bonds per silicon atom.

[0002] In particular, the present invention relates to a process for preparing hydrosilanes by electrochemical reduction of corresponding (pseudo-)halosilanes in the presence of a transition metal complex as a hydride transfer agent, and a protonated (or deuterated) organic base as a source of protons (or deuterium).

[0003] The present invention contributes to a circular economy approach for the silicon element by presenting a process for recycling (pseudo)halosilane compounds, common by-products of silicon chemistry, into higher value-added hydrosilanes. Technical background

[0004] The known methods for transforming silicon-(pseudo)halogen bonds into silicon-hydrogen bonds are based either on:

[0005] - On hydric reagents, used in stoichiometric quantities. The latter These materials exhibit a higher reducing potential than that required by thermodynamics, leading to energy loss in the form of heat. This results in the use of metal hydrides (LiH, NaH, CaH2) or aluminum-boron hydrides (LiAlH4, NaBH4). This method is the preferred one.

[0006] - On borane derivatives (HBpin, BH3 THF) in the presence of catalysts allowing the exchange between group H and X. This route also relies on the use of a stoichiometric reagent and produces an equivalent amount of waste.

[0007] - On the hydrogenolysis of the Si-X bond from a catalyst and a quantity basic stoichiometric, under hydrogen to form a reactive water species as described in JP2016017071A. The bases used are often complex and have a significant cost on the reaction balance.

[0008] - On the hydrogenolysis of the Si-X bond from a heterogeneous catalyst based of rare metals (Ru) and under hydrogen at high temperature as described by WO0039132A1.

[0009] There is therefore a real need for a new synthetic route to produce hydrosilanes efficiently with an improved energy balance compared to known synthetic routes.

[0010] Furthermore, there is a real need for a hydrosilane synthesis route exhibiting high selectivity for hydrosilane products in order to minimize silicon losses in the form of waste compared to known synthesis routes.

[0011] Moreover, there is a real need for a more atom-economical hydrosilane synthesis route by reducing the need for stoichiometric reagents: reducing agents, bases, etc.

[0012] Furthermore, there is a real need for a safer hydrosilane synthesis route, particularly by reducing the quantity and hazard of the reagents used. Summary of the invention

[0013] The present invention is specifically aimed at meeting these needs by providing a process for preparing a hydrosilane of formula (I)

[0014] (R1)o(R2)m(R3)pSiHn

[0015] by electrochemical reduction of a (pseudo-)halosilane of formula (II)

[0016] (R1)o(R2)m(R3)pSiXn

[0017] in which

[0018] - Ri, R2 and R3, identical or different, are a hydrogen atom, a group an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, an alkoxy (-O-alkyl) group whose alkyl group comprises 1 to 12 carbon atoms, a cycloalkoxy (-O-cycloalkyl) group whose cycloalkyl group comprises 3 to 12 carbon atoms, an aryloxy group whose aryl group comprises 6 to 20 carbon atoms, a siloxy (-O-SiRiORnRi2) group in which R1O, Ru, and Rn, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, said alkyl, cycloalkyl, and aryl groups being possibly substituted, a -NR9R4 group, with R9 and R4, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms,an aryl group comprising from 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups possibly being substituted, a silyl group (-SiRioRiiRi2) with R10, Ru and Rn, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups possibly being substituted; ,

[0019] -n is 1,2, 3, 4;

[0020] - m is 0, 1;

[0021] - o is 0, 1;

[0022] - p is 0, 1;

[0023] - X represents Cl, Br, I, -SO2R and -N(SO2R)2 with R being a group -CF3, -CH3 or o-tolyl, m-tolyl, p-tolyl;

[0024] characterized in that in an electrochemical reactor comprising

[0025] - a supporting electrolyte selected from salts - ammonium of formula (NR5R6R7Rs)+ in which R5, R6, R7 and R8, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 6 carbon atoms, or - of alkali metals selected from Li+, Na+, K+, Cs+,

[0026] with derivatives as counter-anions - of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5 SO2O), - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (BAr^J, - of perchlorate (C1O4);

[0027] - at least two electrodes, one of which is an anode and the other a cathode;

[0028] a) contact is made, simultaneously or sequentially, • a (pseudo-)halosilane of formula (II); • a transition metal complex as a hydride transfer agent, the transition metal complex comprising: - a transition metal salt from groups 3 to 12 chosen from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tu, Rh, Pd, Ag, Cd, Ta, W, Re, Os, Ir, Pt, Au, Hg; - one or more transition metal-bound ligands chosen from - nitrogen ligands chosen from 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1-N-diisopropylethylamine (DIPEA or DIEA), bipyridyl (bipy), terpyridine (terpy); phenantroline (phen), ethylenediamine, A,A,A',A'-tetramethylethylenediamine (TMEDA), quinoline and pyridine, - phosphorus ligands, for example, chosen from 1,2-bis(dimethylphosphino)ethane (dmpe), ...dmpe), 1,2-bis(dmpe), 1,2-bis(dmpe), 1, hino)benzene (dmpbz), triphenylphosphine, 2,2'-bis(diphenylphosphino)-l,r-binaphthyl (BINAP), triisopropylphosphine, tris[2-diphenylphosphino)ethyl]phosphine (PP3), 4,5-bis-(di-i-propylphosphinomethyl)acridine, 4,5-bis-(di-phenylphosphinomethyl)acridine, tricyclohexylphosphine, 1,2-bis-diphenylphosphinoethane (dppe), 1,2-bis(diphenylphosphino)ethane (dppb); SPOCOP = (C6H4){ 1,3-OPR2}2 where R is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, 1,3-bis[(di-tert-butylphosphino)oxy]benzene ((tBu)2P-O-C6H4-OP(tBu)2);R PNP = R'2PCH2CH2N(H)CH2CH2PR'2 where R' is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, bis[2-diphenylphosphino)ethyl]amine {((C6H5)2P-CH2-CH2)2NH] and bis[2-di-isopropylphosphino)ethyl]amine {(((CH3)2CH)2P-CH2-CH2)2NH}, ; the carbene ligands chosen from the salts of 1,3-bis(2,6-diisopropylphenyl)-lH-imidazol-3-ium, 1,3-bis(2,6-butyldiisopropylphenyl)-4,5-dihydro-lH-imidazol-3-ium, 1,3-bis(2,4,6-trimethylphenyl)-lH-imidazol-3-ium, 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-lH-imidazol-3-ium, 4,5-dichloro-l,3-bis(2,6-diisopropylphenyl)-lH-imidazol-3-ium, 1,3-di-tert-butyl-lH-imidazol-3-ium, l,3-di-tert-butyl-4,5-dihydro-lH-imidazol-3-ium,

[0029]

[0030] or a combination of these ligands, with derivatives as the counter-anion of sulfonates selected from mesylate or methanesulfonate (CH3SO2O "), triflate or trifluoromethane sulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5 SO2O), halides selected from Cl, Br, I, of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (BAr^J, of perchlorate C1O4; a protonated (or deuterated) organic base with a pKa between 5 and 45 in acetonitrile as a source of protons (or deuterium), obtained by protonation or deuteration of an organic base chosen from - a tertiary amine comprising an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, in particular triethylamine (NEt3), N,N-diisopropylethylamine (DIPEA) and N,N-dicyclohexylmethylamine (Cy2NMe), - an amidine in particular l,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and l,5-diazabicyclo(4.3.0)non-5-ene (DBN). - a guanidine, in particular 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), - a phosphazene, in particular tert-butylimino-tri(pyrrolidino)phosphorane or BTPP, - a proazaphosphatrane, in particular 2,8,9-triisopropyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1 -phosphabicyclo[3.3.3]undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane; a solvent or a mixture of at least two solvent(s) chosen from: - the ethers chosen from diethyl ether, THF, dioxane, anisole, and diglyme, - carbonates selected from dimethyl carbonate, propylene carbonate, and ethylene carbonate, - tertiary amines selected from triethylamine (NEt3), N,N-diisopropylethylamine (DIPEA) and N,N-dicyclohexylmethylamine (Cy2NMe), - nitriles selected from acetonitrile, benzonitrile, - aromatic hydrocarbons selected from benzene, toluene, xylene, - aliphatic hydrocarbons selected from pentane, hexane, cyclohexane, - pyridine-based solvents chosen from pyridine, lutidine, or 2,6-di-tert-butylpyridine, - alkyl halides selected from chloroform and chloride of methylene, dichloromethane, - aryl halides selected from chlorobenzene and dichlorobenzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,2,3,4-tetrafluorobenzene, - ionic liquids chosen from hydrogen sulfate of 1-(4-sulfobutyl)-3-methylimidazolium, l-butyl-3-methylimidazolium chloride ([BMIM]Cl),

[0031] the salts Cl, CF3COO, CF3SO3, (CF3SO2)N, C3F7COO, C4F9SO3, 1-butyl-l-methylpiperidinium of l-butyl-3-methyl imidazolium, the bis-(trifluoromethyl sulfonyl) of l-methyl-3-methyl imidazolium, of l-ethyl-3-methyl imidazolium, of l-ethyl-3-ethyl imidazolium, of l-butyl-3-methyl imidazolium, of 1-isobutyl-3-methyl imidazolium, of l-butyl-3-ethyl imidazolium, of l-methoxyethyl-3-methylimidazolium, of l-methyl-2-methyl-3-ethylimidazolium, of l-trifluoroethyl-3-methyl imidazolium, of l-ethyl-3-ethyl-4-methyl imidazolium, of l-methyl-3-ethyl-4-methyl imidazolium;

[0032] b) a voltage between -0.5 V and -3 V is applied; and

[0033] c) we recover the hydrosilane of formula (I).

[0034] The process of the invention proposes a new synthesis method:

[0035] - more energy-efficient by controlling the reducing potential applied to the preparation of hydrosilanes and thus reduce the over-potentials used; and

[0036] - more economical in atoms by reducing the need for stoichiometric reagents: reducers, bases.

[0037] The present invention also relates to the use of the process of the invention for the recycling of (pseudo-)halosilanes from the corresponding hydrosilanes. Brief description of the figures

[0038] Other features and advantages of the invention will become apparent upon reading the detailed description that follows, for an understanding of which reference should be made to the accompanying drawings in which:

[0039] [Fig. 1] represents the synthesis of a silane from a (pseudo-)halosilane according to the invention. The principle of the process of the invention is based on the production of a metal-hydride transfer agent via the reduction of a metal salt in the presence of a proton source in an organic solvent.

[0040] [Fig.2] represents the two embodiments of the process: a. sequential, b. simultaneous or catalytic.

[0041] [Fig.3] represents the chemical structure of some compounds mentioned in this presentation. Detailed description of the invention

[0042] The present invention relates to a process for preparing a hydrosilane of formula (I)

[0043] (Ri)o(R2)m(R3)PSiHn

[0044] by electrochemical reduction of a (pseudo-)halosilane of formula (II)

[0045] (R1)o(R2)m(R3)pSiXn

[0046] in which

[0047] - Rb R2 and R3, whether identical or different, are a hydrogen atom, a group an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, an alkoxy (-O-alkyl) group whose alkyl group comprises 1 to 12 carbon atoms, a cycloalkoxy (-O-cycloalkyl) group whose cycloalkyl group comprises 3 to 12 carbon atoms, an aryloxy group whose aryl group comprises 6 to 20 carbon atoms, a siloxy (-O-SiRiORnRi2) group in which R1O, Ru, and Rn, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, said alkyl, cycloalkyl, and aryl groups being possibly substituted, a -NR9R4 group, with R9 and R4, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms,an aryl group comprising from 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups possibly being substituted, a silyl group (-SiRioRiiRi2) with R10, Ru and Rn, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups possibly being substituted; ,

[0048] -n is 1,2, 3, 4;

[0049] - m is 0, 1;

[0050] - o is 0, 1;

[0051] - p is 0, 1;

[0052] - X represents Cl, Br, I, -OSO2R and -N(SO2R)2 with R being a group -CF3, -CH3 or o-tolyl, m-tolyl, p-tolyl;

[0053] characterized in that in an electrochemical reactor comprising

[0054] - a supporting electrolyte selected from salts • ammonium of formula (NR5R6R7R8)+ in which R5, R6, R7 and R8, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 6 carbon atoms, or • of alkali metals selected from Li+, Na+, K+, Cs+,

[0055] with derivatives as counter-anions • of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p- toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5 SO2O), • of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (BAr^J, • of perchlorate (C1O4);

[0056] - at least two electrodes, one anode and one cathode;

[0057] a) contact is made, simultaneously or sequentially, • a (pseudo-)halosilane of formula (II); • a transition metal complex as a hydride transfer agent, the transition metal complex comprising: - a transition metal salt from groups 3 to 12 chosen from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tu, Rh, Pd, Ag, Cd, Ta, W, Re, Os, Ir, Pt, Au, Hg; - one or more transition metal-bound ligands chosen from - nitrogen ligands chosen from 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2]octane (DABCO), A-diisopropylethylamine (DIPEA or DIEA), bipyridyl (bipy), terpyridine (terpy); phenantroline (phen), rethylenediamine, AAA',A'-tetramethylethylenediamine (TMEDA), quinoline and pyridine, - the phosphorus ligands chosen from among l,2-bis(dimethylphosphino)ethane (dmpe), l,2-bis(dimethylphosphino)benzene (dmpbz), triphenylphosphine, 2,2'-bis(diphenylphosphino)-l,r-binaphthyl (BINAP), triisopropylphosphine, tris[2-diphenylphosphino)ethyl]phosphine (PP3), 4,5-bis-(di-i-propylphosphinomethyl)acridine, 4,5-bis-(di-phenylphosphinomethyl)acridine, tricyclohexylphosphine, 1,2-bis-diphenylphosphinoethane (dppe), 1,2-bis(diphenylphosphino)ethane (dppb); SPOCOP = (C6H4){ 1,3-OPR2}2 where R is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, 1,3-bis[(di-tert-butylphosphino)oxy]benzene ((tBu)2P-O-C6H4-OP(tBu)2);R PNP = R'2PCH2CH2N(H)CH2CH2PR'2 where R' is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, bis[2-diphenylphosphino)ethyl]amine {((C6H 5)2P-CH2-CH2)2NH] and bis[2-di-isopropylphosphino)ethyl]amine {(((CH3)2 CH)2P-CH2-CH2)2NH], ; - the carbene ligands chosen from the salts of 1,3-bis(2,6-diisopropylphenyl)-lH-imidazol-3-ium, 1,3-bis(2,6-butyldiisopropylphenyl)-4,5-dihydro-lH-imidazol-3-ium, 1,3-bis(2,4,6-trimethylphenyl)- lH-imidazol-3-ium, 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-lH-imidazol-3-ium, 4,5-dichloro-l,3-bis(2,6-diisopropylphenyl)-lH-imidazol-3-ium, 1,3-di-tert-butyl-lH-imidazol-3-ium, l,3-di-tert-butyl-4,5-dihydro-lH-imidazol-3-ium,

[0058] or a combination of these ligands,

[0059] with derivatives as counter-anion - of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5 SO2O), - halides selected from Cl, Br, I, - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr14), - of perchlorate C1O4; • a protonated (or deuterated) organic base with a pKa between 5 and 45 in acetonitrile as a proton (or deuterium) source, obtained by protonation or deuteration of an organic base chosen from - a tertiary amine comprising an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, in particular triethylamine (NEt3), N,N-diisopropylethylamine (DIPEA) and N,N-dicy clohexylmethylamine (Cy2NMe), - an amidine in particular l,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and l,5-diazabicyclo(4.3.0)non-5-ene (DBN). - a guanidine, in particular 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), - a phosphazene, in particular tert-butylimino-tri(pyrrolidino)phosphorane or BTPP, - a proazaphosphatrane, in particular 2,8,9-triisopropyl-2,5,8,9-tetraaza- 1 -phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane; • a solvent or a mixture of at least two solvent(s) chosen from: - the ethers chosen from diethyl ether, THF, dioxane, anisole, and diglyme, - carbonates selected from dimethyl carbonate, propylene carbonate, and ethylene carbonate, - tertiary amines selected from triethylamine (NEt3), N,N-diisopropylethylamine (DIPEA) and N,N-dicyclohexylmethylamine (Cy2 NMe), - nitriles selected from acetonitrile, benzonitrile, - aromatic hydrocarbons selected from benzene, toluene, the xylene, - aliphatic hydrocarbons selected from pentane, hexane, cyclohexane, - pyridine-based solvents chosen from pyridine, lutidine, or 2,6-di-terL-butylpyridine, - alkyl halides selected from chloroform and methylene chloride, dichloromethane, - aryl halides selected from chlorobenzene and dichlorobenzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,2,3,4-tetrafluorobenzene, - ionic liquids chosen from hydrogen sulfate of l-(4-sulfobutyl)-3-methylimidazolium, l-butyl-3-methylimidazolium chloride ([BMIM] Cl),

[0060] the salts Cl, CF3COO , CF3SO3, (CF3SO2)N , C3F7COO, C4F9SO3, 1-butyl-l-methylpiperidinium of l-butyl-3-methyl imidazolium, the bis-(trifluoromethyl sulfonyl) of l-methyl-3-methyl imidazolium, of l-ethyl-3-methyl imidazolium, of l-ethyl-3-ethyl imidazolium, of l-butyl-3-methyl imidazolium, of 1-isobutyl-3-methyl imidazolium, of l-butyl-3-ethyl imidazolium, of l-methoxyethyl-3-methylimidazolium, of l-methyl-2-methyl-3-ethylimidazolium, of l-trifluoroethyl-3-methyl imidazolium, of l-ethyl-3-ethyl-4-methyl imidazolium, of l-methyl-3-ethyl-4-methyl imidazolium;

[0061] b) a voltage between -0.5 V and -3 V is applied; and

[0062] c) we recover the hydrosilane of formula (I).

[0063] As shown in [Fig. 1], the process of the invention makes it possible to generate metal-hydride (MH) species by electrochemical means. These MH species can transfer their hydride to silicon with elimination of the (pseudo)halogen. The reduction of metal salts at the cathode of the electrolyzer leads to the formation of metal species reduced to the ability to react with a proton source to form reactive metal-hydride species.

[0064] To the inventors' knowledge, this synthesis strategy has never been described for the synthesis of main group hydrides.

[0065] As already indicated, the process of the invention makes it possible to control the reduction potential and thus avoid overpotentials and thus be more energy efficient.

[0066] The process of the invention does not require the use of pyrophoric reagents, the handling of which is costly and presents many risks.

[0067] Moreover, the process of the invention generates water species from one proton and two electrons, thus eliminating the need for stoichiometric reagents usually used for the preparation of hydrosilanes.

[0068] For the purposes of the invention, "silane" means a silicon-based molecule having Si-H, Si-D and / or Si-C bonds.

[0069] For the purposes of the invention, the term "hydrosilane" refers to silanes specifically having one or more Si-H bonds.

[0070] For the purposes of the invention, the term "deuterated hydrosilane" refers to silanes specifically exhibiting one or more Si-D bonds.

[0071] For the purposes of the invention, the term "halosilane" refers to silanes specifically having one or more Si-halogen bonds, the halogen being Cl, Br or I

[0072] For the purposes of the invention, the term “pseudo-halosilane” refers to silanes linked to one or more groups which are not halogens but which behave like halogens such as, for example, the groups -OSO2R and -N(SO2R)2 with R being a -CF3, -CH3 or o-tolyl, m-tolyl, p-tolyl group.

[0073] In the context of the present invention, "alkyl" means a linear, branched, and saturated carbon radical, optionally substituted, comprising 1 to 12 carbon atoms. In some cases, the alkyl may comprise, for example, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 6 carbon atoms. Examples of saturated linear or branched alkyl radicals include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, and their branched isomers.

[0074] For the purposes of this invention, "cycloalkyl" means a saturated, optionally substituted, mono- or poly-cyclic carbon radical comprising 3 to 12 carbon atoms. In some cases, the alkyl may comprise, for example, 3 to 10 carbon atoms, or 3 to 6 carbon atoms. Examples of cyclic alkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2,1,1]hexyl, bicyclo[2,2,1]heptyl, bicyclo[3,3,1]nonane, adamantyl, and isopinocampheyl.

[0075] The alkyl and cycloalkyl groups may optionally be substituted by one or more alkoxy groups; one or more aryloxy groups; one or more halogens selected from fluorine, chlorine, bromine or iodine atoms; one or more nitrile groups (-CN); one or more aryl groups; one or more trifluoromethyl groups -(CF3); with the alkoxy and aryl groups as defined within the scope of the present invention.

[0076] The term "aryl" refers to a mono- or polycyclic aromatic substituent comprising from 6 to 20 carbon atoms. The aryl group may comprise, for example, 6 to 10 carbon atoms, or 6 to 8 carbon atoms. The aryl group may comprise, for example, 6 carbon atoms. In the context of the invention, the aryl group may be mono- or polycyclic. By way of example, the following groups may be mentioned: phenyl, benzyl, naphthyl, o-tolyl, m-tolyl, p-tolyl, mesityl, p-nitrophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxybenzyl, p-methoxybenzyl, m-methoxybenzyl, o-methylbenzyl, p-methylbenzyl, and m-methylbenzyl.The aryl group may optionally be substituted by one or more alkoxy groups; one or more aryloxy groups; one or more halogens selected from the atoms of fluorine, chlorine, bromine and iodine; one or more nitrile groups (-CN); one or more trifluoromethyl groups (-CF3); one or more alkyl groups, with the alkoxy and alkyl groups as defined within the scope of the present invention.

[0077] The term "alkoxy" means an alkyl group, as defined above, linked by an oxygen atom (-O-alkyl).

[0078] The term "cycloalkoxy" means a cycloalkyl group, as defined above, linked by an oxygen atom (-O-cycloalkyl).

[0079] The term "aryloxy" means an aryl group, as defined above, linked by an oxygen atom (-O-aryl).

[0080] The term "silyl" designates a substituent of formula -SiRi0RnRi2 with R10, Ru, and R12, identical or different, representing an alkyl, a cycloalkyl, an aryl, a silyl as defined above.

[0081] The term "siloxy" designates a silyl group, as defined above, linked by an oxygen atom (-O- SiRioRnRn)-

[0082] By "halogen" is meant a substituent selected from the atoms of fluorine, chlorine, bromine and iodine or in the form of an anion (also called a halide) selected from F, Cl, Br and I.

[0083] It should be noted that in all compounds, substituents, radicals, groups and subgroups, solvents, reagents, etc. cited, used and / or defined in the context of the present invention, one or more hydrogen atoms can be, possibly replaced by one or more deuterium (2H).

[0084] By “yield” we mean the ratio between the quantity of product obtained and the maximum quantity that would be obtained if the reaction were complete.

[0085] Faradic efficiency (or FE) describes the electrochemical performance of materials by relating the percentage of actual and theoretical products during an electrolysis.

[0086] In the field of catalysis in general, and in the context of the present invention, the term "turnover number" (TON, sometimes translated as "number of rotations") refers to the number of moles of substrate that one mole of catalyst can transform before becoming inactive. A catalyst that does not become inactive would have an infinite "turnover number".

[0087] According to one embodiment of the invention, R2 and R3, identical or different, represent

[0088] - an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 atoms of carbon,

[0089] - a cycloalkyl group comprising 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms,

[0090] - an aryl group comprising from 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms,

[0091] - a siloxy group (-O-SiRioRuRn) of which Rio, Ru and R[2, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms,

[0092] - a silyl group (-SiRi0RnRi2) with R10, Ru and R12, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms,

[0093] - an -NR9R4 group, with R9 and R4, identical or different, representing an atom of hydrogen, an alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms, and an aryl group comprising 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms,

[0094] said alkyl, cycloalkyl and aryl groups being optionally substituted by one or more alkoxy groups, one or more aryloxy groups, one or more halogens chosen from the atoms of fluorine, chlorine, bromine and iodine, one or more nitrile groups (-CN), one or more trifluoromethyl groups (-CF3), one or more alkyl groups, with the alkoxy and alkyl groups as defined within the scope of the present invention.

[0095] According to another embodiment of the invention, n=m=o=p=l.

[0096] According to another embodiment of the invention, n=2 and m=0 and o=p=l.

[0097] According to another embodiment of the invention, n=3, m=o=0 and p=l.

[0098] According to another embodiment of the invention, n=4, m=o=p=0.

[0099] Two embodiments are possible for the process of the invention:

[0100] - sequential, according to which the contacting of the different compounds is effected by steps:

[0101] In a first step, the hydride complex is formed by electrochemical reduction of a metal complex in the presence of a protonated (or deuterated) organic base used as a source of protons (or deuteriums), the (pseudo)halosilane of formula (II) is introduced in a second step and reacts stoichiometrically with the metal hydride formed in the first step;

[0102] or

[0103] - catalytic or simultaneous, according to which the contacting of the different compounds happens simultaneously:

[0104] the different elements of the reaction are mixed in the electrochemical reactor, the electrolysis is then carried out on a catalytic quantity of metal complexes relative to the (pseudo)halosilane of formula (II).

[0105] As shown in [Fig.2], in a process carried out sequentially, the metal complex used as a hydride transfer agent is reduced in the presence of the protonated base used as a proton source, in an organic solvent to form a metal-hydride (MH) species, the (pseudo)halosilane is added in a second step in stoichiometric or over-stoichiometric quantity as appropriate.

[0106] In a simultaneous process also referred to as a catalytic process, the metal complex used as a hydride transfer agent is present in catalytic quantities. It is reduced in the presence of a proton source in an organic solvent to form a metal-hydride (MH) species. The MH reacts with the (pseudo)halosilane present in the reaction mixture to form hydrosilane and the metal salt, which is then re-engaged in a catalytic cycle.

[0107] The process is conducted under an inert atmosphere of nitrogen, argon or a mixture of nitrogen and argon.

[0108] According to one embodiment of the invention, the transition metal complex comprises a transition metal from groups 6 to 11 selected from Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au.

[0109] According to another embodiment of the invention, the transition metal complex comprises a transition metal from groups 7 and 10 selected from Mn, Fe, Co, Ni, Ru, Rh, Pd, Re, Ir, Pt.

[0110] According to one embodiment of the invention, the transition metal complex, also called the metal complex, comprises one or more transition metal-bound ligands selected from the nitrogen ligands chosen from among 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2]octane (DABCO), A-diisopropylethylamine (DIPEA or DIEA), bipyridyl (bipy), terpyridine (terpy); phenantroline (phen), rethylenediamine, AAA',A'-tetramethylethylenediamine (TMEDA), quinoline and pyridine, the phosphorus ligands chosen from 1,2-bis(dimethylphosphino)ethane (dmpe), 1,2-bis(dimethylphosphino)benzene (dmpbz), triphenylphosphine, 2,2'-bis(diphenylphosphino)-1,r-binaphthyl (BINAP), triisopropylphosphine, tris[2-diphenylphosphino)ethyl]phosphine (PP3), 4,5-bis-(di-i-propylphosphinomethyl)acridine, 4,5-bis-(di-phenylphosphinomethyl)acridine, tricyclohexylphosphine, 1,2-bis-diphenylphosphinoethane (dppe), 1,2-bis(diphenylphosphino)ethane (dppb); SPOCOP = (C6H4){ 1,3-OPR2}2 where R is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, 1,3-bis[(di-tert-butylphosphino)oxy]benzene ((tBu)2P-O-C6H4-OP(tBu)2);R PNP = R'2PCH2CH2N(H)CH2CH2PR'2 where R' is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, bis[2-diphenylphosphino)ethyl]amine {((C6H 5)2P-CH2-CH2)2NH] and bis[2-di-isopropylphosphino)ethyl]amine {(((CH3)2 CH)2P-CH2-CH2)2NH], ; [YES]

[0112] or a combination of these ligands, with derivatives as the counter-anion of sulfonates selected from mesylate or methanesulfonate (CH3SO2O "), triflate or trifluoromethane sulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5 SO2O), - halides selected from Cl, Br, I, - of borates selected from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr14),

[0113] of perchlorate C1O4.

[0114] According to another embodiment of the invention, the transition metal complex comprises one or more transition metal-bound ligands selected from - nitrogen ligands chosen from bipyridyl (bipy), terpyridine (terpy); phenantroline (phen), - the phosphorus ligands chosen from among l,2-bis(dimethylphosphino)ethane (dmpe), l,2-bis(dimethylphosphino)benzene (dmpbz), 2,2'-bis(diphenylphosphino)-l,r-binaphthyl (BINAP), tris[2-diphenylphosphino)ethyl]phosphine (PP3),,, 1,2-bis-diphenylphosphino ethane (dppe), 1,2-bis(diphenylphosphino) ethane (dppb); SPOCOP = (C6 H4){ 1,3-OPR2}2 where R is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, 1,3-bis[(di-tert-butylphosphino)oxy]benzene ((tBu)2P-O-C6H4-OP(tBu)2);RPNP = R'2 PCH2CH2N(H)CH2CH2PR'2 where R' is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular bis[2-diphenylphosphino)ethyl]amine {((C6H5)2P-CH2-CH2)2NH] and bis[2-di-isopropylphosphino)ethyl]amine {(((CH3)2CH)2P-CH2-CH2)2NH},

[0115] or a combination of these ligands,

[0116] with derivatives as counter-anion; - of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5 SO2O), - halides selected from Cl, Br, I, - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ( B Ar'4), - of perchlorate C1O4.

[0117] According to one embodiment of the invention, the transition metal complex is cationic and presents derivatives as counter-anions - of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p- toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5 SO2O), - of halides selected from Cl, Br, I, - of borates selected from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr' j, - of perchlorate C1O4.

[0118] According to another embodiment of the invention, the transition metal complex is cationic and presents derivatives as counter-anions - of sulfonates selected from, triflate or trifluoromethane sulfonate (CF3SO2O), - of halides selected from Cl, Br, I, - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAiJ 4).

[0119] When the process is carried out sequentially, the concentration of the metal complex is between 0.1 mmol.l1 and 100 mmol.l1. Preferably, the concentration of the metal complex is between 0.5 mmol.l1 and 25 mmol.l1.

[0120] When the process is carried out sequentially, the stoichiometry in (pseudo)halosilane added during the second step is between 1 and 10 equivalents, preferably between 2 and 4 equivalents, relative to the metal complex.

[0121] In a process, carried out simultaneously or catalytically, the concentration of (pseudo-)halosilane is between 50 mmol.l1 and 300 mmol.l1. Preferably, the concentration of (pseudo-)halosilane is between 100 mmol.l1 and 150 mmol.l*.

[0122] In a process, carried out simultaneously or catalytically, the quantity of transition metal complex is between 0.1 and 100% molar, preferably between 1 and 10% molar, relative to the (pseudo)halosilane of formula (II) whose quantity is defined previously.

[0123] In the process of the invention, the pKa of the protonated (or deuterated) organic base can be between 15 and 35 in acetonitrile. Preferably, the pKa of the base is between 20 and 30 in acetonitrile.

[0124] The protonated (or deuterated) organic base is obtained by protonation or deuteration of an organic base from sulfonic acid: trifluoromethylsulfonic acid (CF3SO3H), methylsulfonic acid (MeSO3H), para-toluenesulfonic acid (p-tolSO3H), tetrafluoroboric acid (HBF4), hexafluorophosphoric acid (HPF6) or hydrochloric acid (HCl), hydrobromic acid (HBr) and hydroiodic acid (HI) (or the corresponding deuterated acids).

[0125] The organic base must be of low nucleophilicity and not react with silicon derivatives.

[0126] In one embodiment of the invention, the organic base is chosen from - an amidine in particular l,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and l,5-diazabicyclo(4.3.0)non-5-ene (DBN). - a guanidine, in particular 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), - a phosphazene, in particular tert-butylimino-tri(pyrrolidino)phosphorane or BTPP, - a proazaphosphatrane, in particular 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-l-pho sphabicy cio [3.3.3] undec ane.

[0127] Preferably, the base used is 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) and 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG).

[0128] When the process is carried out sequentially, the amount of protonated (or deuterated) organic base used as a proton (or deuterium) source is between 0.5 and a large excess relative to the metal complex. Preferably, the amount of protonated organic base is between 1 and 100 equivalents relative to the metal complex.

[0129] In the context of this exposition, what is described for a protonated base applies in the same way to a deuterated base.

[0130] When the process is carried out simultaneously or catalytically, the amount of the protonated (or deuterated) organic base, the proton source, is between 0.1 and 1 equivalent, relative to the (pseudo)halosilane of formula (II). Preferably, the amount of base is 0.5 equivalent relative to the (pseudo)halosilane of formula (II).

[0131] The solvent or mixture of at least two solvent(s) used in the process of the invention may be chosen from - the ethers chosen from diethyl ether, THF, dioxane, anisole, and diglyme, - nitriles selected from acetonitrile, benzonitrile, - alkyl halides selected from chloroform and chloride of methylene, dichloromethane, - aryl halides selected from chlorobenzene and dichlorobenzene, fluorobenzene, 1,2-difluorobenzene, 1,3- difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,2,3,4-tetrafluorobenzene.

[0132] Preferably, the solvent is acetonitrile or 1,2-difluorobenzene.

[0133] The electrochemical reactor or electrolyzer used in the process of The invention may be any reactor known to man. The reactor may be a split cell, an unsplit cell, or a continuous flow cell.

[0134] The electrochemical reactor or electrolyzer used in the process of the invention comprises a support electrolyte selected from salts - ammonium of formula (NR5R6R7R8)+ wherein R5, R6, R7 and R8, identical or different, an alkyl group comprising 1 to 6 carbon atoms and more preferably an alkyl group of 4 carbon atoms, or - of alkali metals selected from Li+, Na+, K+, Cs+,

[0135] with derivatives as counter-anions - of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (BAr^J, - of perchlorate (C1O4).

[0136] Preferably, the supporting electrolyte is LiClO4 or tetrabutylammonium trifluoromethylsulfonate (TBAOTf).

[0137] The concentration of the supporting electrolyte is between 0.01 mol.l1 and 5 mol.l1. Preferably, it is between 0.05 mol.l1 and 0.25 mol.l1. Even more preferably, the concentration of the supporting electrolyte is 0.1 mol.l1.

[0138] The supporting electrolyte can be the solvent if the latter is an ionic liquid.

[0139] The electrochemical reactor or electrolyzer used in the process of the invention also includes at least two electrodes, one of which is an anode and the other a cathode.

[0140] The cathode can be chosen from common materials such as platinum, gold, or carbon-based materials such as vitreous carbon, graphite carbon, or boron-doped diamond (BDD). Preferably, the cathode is made of vitreous carbon.

[0141] The anode may be sacrificial (or galvanic) and be chosen from common materials such as magnesium, aluminum, or zinc, or it may be non-sacrificial and chosen from common materials such as platinum, gold, or carbon-based materials such as vitreous carbon, graphite carbon, or boron-doped diamond (BDD). Preferably, the anode is composed of magnesium, aluminum, or zinc.

[0142] The electrochemical or electrolysis process can be carried out at constant potential (potentiostatic) or at constant current (galvanostatic) against a reference electrode.

[0143] The reference electrode, which has the role of maintaining a practically invariant potential under the conditions prevailing in an electrochemical measurement, is a silver wire electrode.

[0144] According to one embodiment of the invention, the process is carried out at a constant potential between -0.5 V and -3 V (vs ferrocene or Fc0 / +), and preferably between -1.3 V and -2.5 V.

[0145] According to another embodiment of the invention, the process is carried out at a constant potential at the reduction potential of the metal complex.

[0146] When the process is carried out simultaneously or catalytically, a quantity of charge of between 0.1 and 10 equivalents, preferably between 0.1 and 5 equivalents, more preferably between 0.1 and 2 equivalents of electrons, with respect to the (pseudo)halosilane of formula (II) is passed.

[0147] According to one embodiment the process is carried out simultaneously or catalytically by passing a quantity of charge 2 equivalents of electrons, relative to the (pseudo)halosilane of formula (II).

[0148] When the process is carried out sequentially, a charge quantity of between 0.1 and 10 electron equivalents relative to the metal complex is transferred. Preferably, the charge quantity is between 1.5 and 2.1 electron equivalents relative to the metal complex.

[0149] According to one embodiment the process is carried out sequentially by passing a quantity of charge of 2 equivalents of electrons with respect to the metal complex.

[0150] The reaction temperature is between -78°C and 150°C, preferably between 0°C and 40°C, more preferably 25°C.

[0151] The present invention makes it possible to work in conditions considered mild, temperatures below 150°C, atmospheric pressure.

[0152] When the process is carried out sequentially, the (pseudo)halosilane of formula (II) is added during the second step.

[0153] The application of the process of the invention is integrated into recycling processes for (pseudo-)halosilanes derived from the use of the corresponding hydrosilanes. Thus, the present invention also relates to the use of the process of the invention for the recycling of (pseudo-)halosilanes derived from the corresponding hydrosilanes. EXAMPLES

[0154] All reactions and electrolysis are carried out under a strict atmosphere of ultrapure argon or nitrogen (< 1 ppm oxygen or water), using an MBraun LabMaster DP type glove box. The glassware and magnetic bars are dried for at least 2 hours at 60°C for the NMR tubes and 120°C for the rest. before use. The various products used were purchased from Sigma Aldrich with the exception of the deuterated solvents purchased from Eurisotop and 1,2-difluorobenzene purchased from Fluorochem.

[0155] The solvents are dried by standard methods and distilled immediately before use or stored on a 3 Å molecular sieve. This molecular sieve is dried under vacuum at 250 °C for 24 hours before use. The supporting electrolyte salts are of the highest available quality, dried under vacuum at 80 °C for 24 hours before use, and stored under inert conditions. All other reagents are dried or degassed before use.

[0156] Electrolysis is carried out with a VersaStat4 potentiostat using VersaStudio software.

[0157] In the examples, the electrolytic cell used consists of a glass reactor with a volume of 5 ml (model IKA ElectraSyn 2.0), the cathode, also called the working electrode, is made of vitreous carbon and was purchased from IKA, the reference electrode, purchased from IKA, is a silver wire in a glass capillary tube with a frit filled with the support electrolyte salt solution in the selected solvent, the sacrificial counter electrode is made of magnesium and was purchased from IKA or of aluminium and was purchased from.

[0158] The NMR spectra of elements 'H and 31P were acquired using a Bruker AVANCE Neo 400 MHz spectrometer at 25°C. GC-MS analyses were performed using a Shimadzu GC-2010 Ultra Gas chromatograph equipped with a Supelco SLB-ms silica capillary column. A calibration curve was generated for each hydrosilane product. Synthesis of new compounds

[0159] • [Pt(dmpbz)2](BPh4)2

[0160] Under an inert argon atmosphere, a solution of 1,2-bis(dimethylphosphino)benzene (310 mg, 1.56 mmol, 2.43 equivalents) in acetonitrile (2 mL) is added to a stirred suspension of bis(benzonitrile)platinum dichloride (303 mg, 0.64 mmol, 1.00 equivalents) in acetonitrile (3 mL), resulting in a color change of the solid from yellow to white. After 1 h, the solvent is evaporated under vacuum and the solid is washed twice with 2 mL of diethyl ether, then resuspended by adding acetonitrile (5 mL). Next, a solution of sodium tetraphenylborate (439 mg, 1.28 mmol, 2.00 equivalents) in acetonitrile (2 mL) is added. After 12 hours of stirring, the resulting solution is filtered to remove the NaCl formed. The solvent is evaporated under vacuum, and the solid is washed twice with 2 mL of diethyl ether. The product is purified by recrystallization in acetonitrile and dried under vacuum, resulting in a yield of 48% (380 mg). • MTBD.HOTf

[0161] Under an inert argon atmosphere, a solution of trifluoromethylsulfonic acid (1.0 mL, 11.3 mmol, 1 equivalent) in diethyl ether (5 mL) is added by syringe to a solution of MTBD (150 µL, 11.4 mmol, 1.01 equivalents) in diethyl ether (15 mL) with rapid stirring at 0 °C. The product precipitates as colorless crystals, which are separated from the liquid phase by decantation. The solid is washed twice with 5 mL of diethyl ether and then dried under vacuum for 12 h. The product is obtained in a yield of 70% (2.44 g). • BTMGHOTf

[0162] Under an inert argon atmosphere, a solution of trifluoromethylsulfonic acid (1.0 mL, 11.3 mmol, 1 equivalent) in diethyl ether (5 mL) is added by syringe to a solution of BTMG (1935 mg, 11.3 mmol, 1.0 equivalent) in diethyl ether (10 mL) with rapid stirring at 0 °C. The product precipitates as colorless crystals, which are separated from the liquid phase by decantation. The solid is washed twice with 5 mL of diethyl ether and then dried under vacuum for 12 h. The product is obtained with a yield of 94% (3.4 g). Sequential synthesis - General operating procedure

[0163] The reaction is conducted under an inert atmosphere (argon or nitrogen). In an electrolytic cell equipped with a magnetic stir bar, a working electrode (cathode), a reference electrode, and a sacrificial counter electrode (anode), the metal complex, the background salt, the proton source (Xi equivalents), and a solvent are added. At temperature (T) and with stirring, a current is passed, fixing the potential between the working electrode and the reference electrode (E). Electrolysis is maintained until the desired amount of charge (C) has passed through. The formation of the hydride complex is monitored by NMR. Subsequently, a quantity of (pseudo-)halosilane (X2 equivalents) is added to the solution containing the hydride complex formed previously. The formation of the hydride complex is monitored by NMR. The hydrosilane yield is then obtained by GC-MS. Example 1:

[0164] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.4 mM, 1 equivalent), MTBD HOTf (6.3 mg, 8.3 mM, 1.5 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current corresponding to 2.4 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a 99% conversion of the complex initially added to the reaction.

[0165] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl trifluoromethanesulfonate (TMSOTf) (5.5 pmol, 2 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 27% hydrosilane was obtained. Example 2:

[0166] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.4 mM, 1 equivalent), MTBD HOTf (6.3 mg, 8.3 mM, 1.5 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current corresponding to 2.4 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 99% of the complex initially added to the reaction.

[0167] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl iodide (TMSI) (7.0 pmol, 2.6 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 31% hydrosilane was obtained. Example 3:

[0168] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.4 mM, 1 equivalent), MTBD HOTf (6.3 mg, 8.3 mM, 1.5 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current corresponding to 2.4 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 99% of the complex initially added to the reaction.

[0169] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl bromide (TMSBr) (6.1 pmol, 2.3 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 12% hydrosilane was obtained. Example 4:

[0170] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.4 mM, 1 equivalent), MTBD HOTf (6.3 mg, 8.3 mM, 1.5 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current corresponding to 2.4 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 99% of the complex initially added to the reaction.

[0171] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Triethylsilyl trifluoromethanesulfonate (TESOTf) (5.8 pmol, 2.1 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 21% hydrosilane was obtained. Example 5:

[0172] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, LiC104 (27.0 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.3 mM, 1 equivalent), BTMGHOTf (7.3 mg, 9.09 mM, 1.7 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current of 2.5 C is passed through the working electrode. The formation of the hydride complex is observed quantitatively by NMR with respect to the applied electrical charge, corresponding to a conversion of more than 99% of the complex initially added to the reaction.

[0173] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl trifluoromethanesulfonate (TMSOTf) (6.6 pmol, 2.5 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 9% hydrosilane was obtained. Example 6:

[0174] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, LiC104 (27.0 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.3 mM, 1 equivalent), BTMGHOTf (7.3 mg, 9.09 mM, 1.7 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current corresponding to 2.5 C is passed through the working electrode. The formation of The hydride complex is observed by NMR in a quantitative manner with respect to the electrical charge passed, corresponding to a conversion greater than 99% of the complex initially added to the reaction.

[0175] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Triethylsilyl trifluoromethanesulfonate (TESOTf) (7.7 pmol, 2.9 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 7% hydrosilane was obtained. Example 7:

[0176] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, LiC104 (27.0 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.3 mM, 1 equivalent), BTMGHOTf (7.3 mg, 9.09 mM, 1.7 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current of 2.5 C is passed through the working electrode. The formation of the hydride complex is observed quantitatively by NMR with respect to the applied electrical charge, corresponding to a conversion of more than 99% of the complex initially added to the reaction.

[0177] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl bromide (TMSBr) (7.6 pmol, 2.8 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 25% hydrosilane was obtained. Example 8:

[0178] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial magnesium counter electrode, LiC104 (27.0 mg, 0.1 M), [Pt(dmpe)2](BPh4)2 (15.2 mg, 5.3 mM, 1 equivalent), BTMGHOTf (7.3 mg, 9.09 mM, 1.7 equivalents), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.8 V is applied relative to the reference electrode, and a current of 2.5 C is passed through the working electrode. The formation of the hydride complex is observed quantitatively by NMR with respect to the applied electrical charge, corresponding to a conversion of more than 99% of the complex initially added to the reaction.

[0179] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Triethylsilyl trifluoromethanesulfonate (TESOTf) (6.2 pmol, 2.3 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 5% hydrosilane was obtained. Example 9:

[0180] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), MTBD HOTf (12 mg, 15.8 mM, 3.1 equivalent), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.55 V is applied relative to the reference electrode, and a current corresponding to 2.6 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 90% of the complex initially added to the reaction.

[0181] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl trifluoromethanesulfonate (TMSOTf) (5.5 pmol, 2.4 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 17% hydrosilane was obtained. Example 10:

[0182] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), MTBD HOTf (12 mg, 15.8 mM, 3.1 equivalent), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.55 V is applied relative to the reference electrode, and a current corresponding to 2.6 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 90% of the complex initially added to the reaction.

[0183] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl iodide (TMSI) (7.0 pmol, 3.1 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 36% hydrosilane was obtained. Example 11:

[0184] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and a sacrificial aluminum counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), MTBD HOTf (12 mg, 15.8 mM, 3.1 equivalent), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.55 V is A current of 2.6 C is applied relative to the reference electrode and passed through the working electrode. The formation of the hydride complex is observed quantitatively by NMR with respect to the electrical charge passed, corresponding to a 90% conversion of the complex initially added to the reaction.

[0185] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl bromide (TMSBr) (7.6 pmol, 3.3 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 11% hydrosilane was obtained. Example 12:

[0186] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), MTBD HOTf (12 mg, 15.8 mM, 3.1 equivalent), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.55 V is applied relative to the reference electrode, and a current corresponding to 2.6 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 90% of the complex initially added to the reaction.

[0187] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Triethylsilyl trifluoromethanesulfonate (TESOTf) (8.8 pmol, 3.9 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 30% hydrosilane was obtained. Example 13:

[0188] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), BTMG HOTf (12.3 mg, 15.3 mM, 3.1 equivalent), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.55 V is applied relative to the reference electrode, and a current corresponding to 2.7 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 88% of the complex initially added to the reaction.

[0189] A volume of 0.5 ml of the prepared platinum hydride complex solution is taken. Trimethylsilyl trifluoromethanesulfonate (TMSOTf) (11.1 pmol, 4.9 eq / PtH) is added to this sample. The mixture is stirred for 2 hours at 22°C. A yield of 24% hydrosilane was obtained. Example 14:

[0190] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), BTMGHOTf (12.3 mg, 15.3 mM, 3.1 equivalent), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.55 V is applied relative to the reference electrode, and a current corresponding to 2.7 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 88% of the complex initially added to the reaction.

[0191] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl iodide (TMSI) (10.5 pmol, 4.7 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 32% hydrosilane was obtained. Example 15:

[0192] In an electrolytic cell (5 ml) equipped with a magnetic stir bar, a glassy carbon working electrode, a reference electrode (silver wire), and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), BTMG HOTf (12.3 mg, 15.3 mM, 3.1 equivalent), and 2.5 ml of dry acetonitrile are added under an inert atmosphere. With stirring, a potential of -1.55 V is applied relative to the reference electrode, and a current corresponding to 2.7 C is passed through the working electrode. The formation of the hydride complex is observed by NMR quantitatively with respect to the electrical charge passed, corresponding to a conversion of 88% of the complex initially added to the reaction.

[0193] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Trimethylsilyl bromide (TMSBr) (10.6 pmol, 4.7 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 10% hydrosilane was obtained. Example 16:

[0194] In an electrolytic cell (5 ml) equipped with a magnetic rod, a glassy carbon working electrode, a reference electrode (silver wire) and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (98 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (15.5 mg, 5.0 mM, 1 equivalent), BTMGHOTf (12.3 mg, 15.3 mM, 3.1 equivalent), and 2.5 mL of dry acetonitrile under an inert atmosphere. With stirring, a potential of -1.55 V was applied relative to the reference electrode, and a current of 2.7 C was passed through the working electrode. The formation of the hydride complex was observed quantitatively by NMR with respect to the applied electrical charge, corresponding to an 88% conversion of the complex initially added to the reaction.

[0195] A 0.5 mL aliquot of the prepared platinum hydride complex solution is taken. Triethylsilyl trifluoromethanesulfonate (TESOTf) (10.6 pmol, 4.7 eq / PtH) is added to this aliquot. The mixture is stirred for 2 h at 22 °C. A yield of 18% hydrosilane was obtained. Catalytic synthesis - General operating procedure

[0196] The reaction is conducted under an inert atmosphere (argon or nitrogen). In an electrolytic cell equipped with a magnetic stir bar, a working electrode (cathode), a reference electrode, and a sacrificial counter electrode (anode), the metal complex, the background salt, the proton source (Xi equivalents), the (pseudo-)halosilane (X2 equivalents), and a solvent are added. At temperature (T) and with stirring, a current is passed, fixing the potential between the working electrode and the reference electrode (E). Electrolysis is maintained until the desired amount of charge (C) has passed through. The hydrosilane yield is obtained by GC-MS or NMR. Example 17#:

[0197] In an electrolytic cell (5 ml) equipped with a magnetic rod, a glassy carbon working electrode, a reference electrode (silver wire) and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (114 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (10.3 mg, 2.8 mM, 1 equivalent), MTBD HOTf (57.1 mg, 63 mM, 22.5 equivalent), trimethylsilyl trifluoromethanesulfonate (TMSOTf) (67 µl, 124 mM, 44.2 eq) and 3 ml of dry acetonitrile are added under an inert atmosphere. Under stirring, a potential of -1.5 V is applied relative to the reference electrode, and a current corresponding to 31.4 C is passed through the working electrode. Hydrosilane is obtained with a TON of 4.1 per Pt and a faradaic efficiency of 21%. Example 18#:

[0198] In an electrolytic cell (5 ml) equipped with a magnetic rod, a glassy carbon working electrode, a reference electrode (silver wire) and a sacrificial magnesium counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (118 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (10 mg, 2.7 mM, 1 equivalent), BTMG HOTf (56.1 mg, 58 mM, 21.5 equivalent), and [Pt(dmpbz)2](BPh4)2 (10 mg, 2.7 mM, 1 equivalent), are added Trimethylsilyl iodide (TMSI) (51 µl, 99 mM, 36.4 eq) and 3 mL of dry acetonitrile were mixed under an inert atmosphere. With stirring, a potential of -1.75 V was applied relative to the reference electrode, and a current corresponding to 13 C was passed through the working electrode. Hydrosilane was obtained with a TON of 2.4 per Pt and a faradaic efficiency of 30%. Example 19#:

[0199] In an electrolytic cell (5 ml) equipped with a magnetic rod, a glassy carbon working electrode, a reference electrode (silver wire) and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (118 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (2.4 mg, 0.6 mM, 1 equivalent), MTBD HOTf (58.5.1 mg, 64 mM, 21.5 equivalent), trimethylsilyl trifluoromethanesulfonate (TMSOTf) (70 pl, 129 mM, 198 eq) and 3 ml of dry 1,2-difluorobenzene are added under an inert atmosphere. Under stirring, a potential of -1.5 V is applied relative to the reference electrode, and a current corresponding to 14.2 C is passed through the working electrode. Hydrosilane is obtained with a TON of 7.9 per Pt and a faradaic efficiency of 27%. Example 20#:

[0200] In an electrolytic cell (5 ml) equipped with a magnetic rod, a glassy carbon working electrode, a reference electrode (silver wire) and an aluminum sacrificial counter electrode, tetrabutylammonium trifluoromethanesulfonate (nBu4NOTf) (118 mg, 0.1 M), [Pt(dmpbz)2](BPh4)2 (5.2 mg, 1.5 mM, 1 equivalent), BTMG HOTf (87 mg, 90 mM, 64.1 equivalent), triethylsilyl trifluoromethanesulfonate (TESOTf) (121 pl, 178 mM, 126.6 eq) and 3 ml of dry 1,2-difluorobenzene are added under an inert atmosphere. Under stirring, a potential of -1.75 V is applied relative to the reference electrode, and a current corresponding to 14.7 C is passed through the working electrode. Hydrosilane is obtained with a TON of 6.7 per Pt and a faradaic efficiency of 37%.

[0201] The results obtained by the sequential synthesis (examples 1 to 20) are presented in Table 1.

[0202] [Tables 1] Ex Bas®HX OO Aftôàè EO Chasse O} axori O) T PWW MT8I3 HOTf H 4) nfôiWH | Oi T8 24 TMsem on W ? Rldmpci, MT BD Hem nB^NOTf iW ■T8 2,4 TMS) OS) 31 3 HOTf rRNOT Oi 0.8 24 TMSB (2.3) 12 O MTSO HOTf ......Lié)...... nByNOTf | ■1.8 24 TKSOTf on 21 5 lïkl âRy STæ HOTf O?) Mg 08 2.S TM SOT (2.5) S 6 PiWnssek BTMG HOTf 07) ucg Mg 08 AS TMS) (20 7 7 PigtwO BTMG HOTf O?) uciq Mil 08 2.5 WBt 08) 25 S æp^n SW HOTf GO ucq Mg T.8 2.5 ■TESCW (2.3) 5 3 RfcOptO( SPIfe MTBD HOT on nB^NOTf Al 4 SB 2.8 TMSOTt (2.4) 17 10 HOTf 430 . nfî^NOTf Ai G SB 24 TUS) (30 38 11 HOTf ............ nB^NPTf Al 4.55 2 8 WSB? 0-3) O- à P^mpbsy MTS0 HO H (3 H riB^NOT Al ■185 2.8 TESOT 35 13 14 15 16 PfftOpfcOi $(¾ P^mp^T ER) / ' PliXOptOf BTMG ■J à 1 MG HOTf (3-0 “'STMG™ HQTf HtwT HOTf oo nBiiNQTf nBuNÔTf nBq;N OTf nB^NOTf Ai Al Ai Ai: ■$ gg; 24 W 18

[0203] In Table 1, "yield" means the ratio between the amount of product obtained and the maximum amount that would be obtained if the reaction were complete.

[0204] The results obtained by catalytic synthesis (examples 21-24) are presented in Table 2.

[0205] [Tables2] Es BaseHX Ansjds £(Vi CWgs O Efficiency FarsbitW W ax (¾) TON ([SR w : 17 Pt(dmpbz) MTBO hou .1^5)............ AI -1.5 31.4 21 TMSOB [44.2.5 4.1 18 Pt(dmpbz| (BPh)g BTMG HOTf (21 61 W -1.75 13 TMSi (44.1) 2.4 19 (“, MTBD HOTt <99) Al -1.5 14.2 2 TMSOH 7.9 20 Pt(dmpbz| (BRÿg BTMG HOTf (64.1) AI -1.75 14.8 57 TESOTf (128.6) 6.7

[0206] Some abbreviations used in the context of the present invention are indicated below:

[0207] TBD: l,5,7-Triazabicyclo[4.4.0]dec-5-ene

[0208] MTBD: 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene

[0209] BTMG: 2-tert-butyl-1,1,3,3-tetramethylguanidine

[0210] TBAOTf: tetra-n-butylammonium trifluoromethylsulfonate

[0211] Fc0 / +: ferrocene / ferrocenium couple

[0212] TON: Turnover Number

Claims

1. Demands Process for preparing a hydrosilane of formula (I) (Ri)o(R2)m(R3)PSiHn by electrochemical reduction of a (pseudo-)halosilane of formula (II) (Ri)o(R2)m(R3)PSiXn in which - Rb, R2, and R3, whether identical or different, represent a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkoxy (-O-alkyl) group with an alkyl group with 1 to 12 carbon atoms, a cycloalkoxy (-O-cycloalkyl) group with a cycloalkyl group with 3 to 12 carbon atoms, an aryloxy group with an aryl group with 6 to 20 carbon atoms, and a siloxy (-O-SiRioRnRi2) group. R10, Ru, and Rn, whether identical or different, represent a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, and an aryl group with 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups possibly being substituted, a -NR9R4 group, with R9 and R4, identical or different, representing a hydrogen atom,an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups being optionally substituted, a silyl group (-SiRioRi 1R12) with R10, Ru and Rn, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups being optionally substituted; - n is 1, 2, 3, 4; - m is 0, 1; - o is 0, 1; - p is 0, 1; - X represents Cl, Br, I, -OSO2R and -N(SO2R)2 with R being a group -CF3, -CH3 or o-tolyl, m-tolyl, p-tolyl; characterized in that in an electrochemical reactor comprising - a supporting electrolyte selected from salts - ammonium of formula (NR5R6R7R8)+ in which R5, R6, R7 and R8, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 6 carbon atoms, or - of alkali metals selected from Li+, Na+, K+, Cs+, with derivatives as the counter-anion - of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5SO2O), - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr1^), - of perchlorate (C1O4); - at least two electrodes, one anode and one cathode; a) contact is made, simultaneously or sequentially, • a (pseudo-)halosilane of formula (II); • a transition metal complex as a hydride transfer agent, the transition metal complex comprising: - a transition metal salt from groups 3 to 12 chosen from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tu, Rh, Pd, Ag, Cd, Ta, W, Re, Os, Ir, Pt, Au, Hg; - one or more transition metal-bound ligands chosen from - nitrogen ligands chosen from 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2]octane (DABCO), α-diisopropylethylamine (DIPEA or DIEA), bipyridyl (bipy), terpyridine (terpy); phenanthroline (phen), ethylenediamine, MMA^W'-tetramethylethylenediamine (TMEDA), quinoline and pyridine, phosphorus ligands selected from 1,2-bis(dimethylphosphino)ethane (dmpe), 1,2-bis(dimethylphosphino)benzene (dmpbz), triphenylphosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), triisopropylphosphine, tris[2-diphenylphosphino)ethyl]phosphine (PP3), 4,5-bis-(di-1-propylphosphinomethyl)acridine, 4,5-bis-(di-phenylphosphinomethyl)acridine, tricyclohexylphosphine, 1,2-bis-diphenylphosphinoethane (dppe), the 1,2-bis(diphenylphosphino)ethane (dppb); SPOCOP = (C6H4){1,3-OPR2}2 where R is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, 1,3-bis[(di-tert-butylphosphino)oxy]benzene ((tBu)2P-O-C6H4-OP(tBu)2);R PNP = R'2PCH2CH2 N(H)CH2CH2PR'2 where R' is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, bis[2-diphenylphosphino)ethyl]amine {((C6H5)2P-CH2-CH2)2NH} and bis[2-di-isopropylphosphino)ethyl]amine {(((CH3)2 CH)2P-CH2-CH2)2NH},; the carbene ligands chosen from the salts of 1,3-bis(2,6-diisopropylphenyl)-lH-imidazol-3-ium, 1,3-bis(2,6-butyldiisopropylphenyl)-4,5-dihydro-lH-imidazol-3-ium, 1,3-bis(2,4,6-trimethylphenyl)-lH-imidazol-3-ium, 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazol-3-ium, 4,5-dichloro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-3-ium, 1,3-di-tert-butyl-1H-imidazol-3-ium, 1,3-di-tert-butyl-4,5-dihydro-lH-imidazol-3-ium, or a combination of these ligands, with derivatives as the counter-anion of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5SO2O), halides selected from Cl, Br, I, of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr14), of perchlorate C1O4; a protonated (or deuterated) organic base with a pKa between 5 and 45 in acetonitrile as a proton (or deuterium) source, obtained by protonation or deuteration of an organic base chosen from a tertiary amine comprising an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, notably triethylamine (NEt3), N,N-diisopropylethylamine (DIPEA) and N,N-dicyclohexylmethylamine (Cy2NMe), an amidine in particular l,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and l,5-diazabicyclo(4.3.0)non-5-ene (DBN). a guanidine, in particular 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), a phosphazene, in particular tert-butylimino-tri(pyrrolidino)phosphoane or BTPP, a proazaphosphatrane, in particular 2,8,9-triisopropyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1 -phosphabicyclo [3. 3.3]undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane; • a solvent or a mixture of at least two solvent(s) chosen from: - the ethers chosen from diethyl ether, THF, dioxane, anisole, and diglyme, - carbonates selected from dimethyl carbonate, propylene carbonate, and ethylene carbonate, - tertiary amines selected from triethylamine (NEt3), N,N-diisopropylethylamine (DIPEA) and N,N-dicyclohexylmethylamine (Cy2NMe), - nitriles selected from acetonitrile, benzonitrile, - aromatic hydrocarbons selected from benzene, the toluene, xylene, - aliphatic hydrocarbons selected from pentane, hexane, cyclohexane, - pyridine-based solvents chosen from pyridine, lutidine, or 2,6-di-tert-butylpyridine, - alkyl halides selected from chloroform and methylene chloride, dichloromethane, - aryl halides selected from chlorobenzene and dichlorobenzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,2,3,4-tetrafluorobenzene, - ionic liquids chosen from hydrogen sulfate of l-(4-sulfobutyl)-3-methylimidazolium, 1-butyl-3-methylimidazolium chloride ([BMIM] Cl), the salts CF, CF3COO , CF3SO3, (CF3SO2)N, C3F7COO, C4F9SO3 , 1-butyl-l-methylpiperidinium of l-butyl-3-methyl imidazolium, the bis-(trifluoromethyl sulfonyl) of l-methyl-3-methyl imidazolium, of l-ethyl-3-methyl imidazolium, of l-ethyl-3-ethyl imidazolium, of l-butyl-3-methyl imidazolium, of l-isobutyl-3-methyl imidazolium, of l-butyl-3-ethyl imidazolium, of l-methoxyethyl-3-methylimidazolium, of l-methyl-2-methyl-3-ethylimidazolium, of l-trifluoroethyl-3-methyl imidazolium, of l-ethyl-3-ethyl-4-methyl imidazolium, of l-methyl-3-ethyl-4-methyl imidazolium; b) a voltage between -0.5 V and -3 V is applied; and c) the hydrosilane of formula (I) is recovered.

2. A process according to claim 1, characterized in that Rb, R2, and R3, identical or different, represent: - an alkyl group comprising 1 to 12 carbon atoms, - a cycloalkyl group comprising 3 to 12 carbon atoms, - an aryl group comprising 6 to 20 carbon atoms, - a siloxy group (-O-SiRioRnRn) wherein R10, Ru, and R2, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, - a silyl group (-SiRi0RnRi2) with R10, Ru, and R12, identical or different, representing a hydrogen atom, an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, - a -NR9R4 group, with R9 and R4, identical or different, representing a hydrogen atom,an alkyl group comprising 1 to 12 carbon atoms, a cycloalkyl group comprising 3 to 12 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, said alkyl, cycloalkyl and aryl groups being optionally substituted.

3. A process according to any one of claims 1 or 2, characterized in that it is carried out in a sequential manner, according to which the contact of the different compounds is made in stages: in a first stage, the hydride complex is formed by electrochemical reduction of a metal complex in the presence of a protonated (or deuterated) organic base used as a source of protons (or deuteriums), the (pseudo)halosilane of formula (II) is introduced in a second stage and reacts stoichiometrically with the metal hydride formed in the first stage; or in a catalytic or simultaneous manner, according to which the contact of the different compounds is made simultaneously: the different elements of the reaction are mixed in the electrochemical reactor, electrolysis is then carried out on a catalytic quantity of metal complexes relative to the (pseudo)halosilane of formula (II).

4.

5. A process according to any one of claims 1 to 3, characterized in that the transition metal complex comprises a transition metal from groups 7 and 10 selected from Mn, Fe, Co, Ni, Ru, Rh, Pd, Re, Ir, Pt. A method according to any one of claims 1 to 4, characterized in that the transition metal complex comprises one or more transition metal-bound ligands selected from - nitrogen ligands chosen from bipyridyl (bipy), terpyridine (terpy); phenantroline (phen), - the phosphorus ligands chosen from 1,2-bis(dimethylphosphino)ethane (dmpe), 1,2-bis(dimethylphosphino)benzene (dmpbz), 2,2'-bis(diphenylphosphino)-l,l'-binaphthyl (BINAP), tris[2-diphenylphosphino)ethyl]phosphine (PP3), 1,2-bis-diphenylphosphinoethane (dppe), 1,2-bis(diphenylphosphino)ethane (dppb); SPOCOP = (C6H 4){ 1,3-OPR2}2 where R is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, 1,3-bis[(di-tert-butylphosphino)oxy]benzene ((tBu)2P-O-C6H4-OP(t Bu)2); R PNP = R'2PCH2CH2N(H)CH2CH2PR'2 where R' is an aryl group with 6 to 20 carbon atoms such as phenyl or an alkyl group with 1 to 12 carbon atoms such as tert-butyl and isopropyl, in particular, bis[2-diphenylphosphino)ethyl]amine {((C6H5)2P-CH2-CH2)2NH} and bis[2-di-isopropylphosphino)ethyl]amine {(((CH3)2CH)2P-CH2-CH2)2NH}, or a combination of these ligands, with derivatives as the counter-anion - of sulfonates selected from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), tosylate or p-toluenesulfonate (CH3C6H4SO2O), besylate or benzenesulfonate (C6H5SO2O), - halides selected from Cl, Br, I, - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BAr14), - of perchlorate C1O4.

6. A process according to any one of claims 1 to 5, characterized in that when the process is carried out sequentially, - the concentration of the metal complex is between 0.1 mmol / L and 100 mmol / L*, and - the stoichiometry of (pseudo)halosilane added during the second step is between 1 and 10 equivalents with respect to the metal complex.

7. A process according to any one of claims 1 to 5, characterized in that when the process is carried out simultaneously or catalytically, - the concentration of (pseudo-)halosilane is between 50 mmol / L and 300 mmol / L, and - the amount of transition metal complex is between 0.1 and 100% molar, relative to (pseudo)halosilane.

8. A method according to any one of claims 1 to 7, characterized in that the organic base is selected from - an amidine in particular 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and 1,5-diazabicyclo(4.3.0)non-5-ene (DBN). - a guanidine, in particular 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), - a phosphazene, in particular tert-butylimino-tri(pyrrolidino)phosphorane or BTPP, - a proazaphosphatrane, in particular 2,8,9-triisopropyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane, 2,8,9-triisobutyl-2,5,8,9-tetraaza-l-phosphabicyclo[3. 3.3]undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-l-pho shabic y cio [3.3.3] undecane.

9. A process according to any one of claims 1 to 6 and 8, characterized in that when the process is carried out sequentially, the amount of the organic base is between 0.5 and a large excess relative to the metal complex.

10. A process according to any one of claims 1 to 5, 7 and 8, characterized in that when the process is carried out simultaneously or catalytically, the amount of the organic base, proton source, is between 0.1 and 1 equivalent, relative to the (pseudo)halosilane of formula (II).

11. A process according to any one of claims 1 to 10, characterized in that the solvent or mixture of at least two solvent(s) used in the process of the invention are chosen from acetonitrile or 1,2-difluorobenzene.

12. A method according to any one of claims 1 to 11, characterized in that the supporting electrolyte is selected from ammonium salts of formula (NR5R6R7R8) in which R5, R6, R7R8 and R8, identical or different, an alkyl group comprising 1 to 6 carbon atoms and more preferably an alkyl group of 4 carbon atoms, or - of alkali metals chosen from Li+, Na+, K+, Cs+, with as counter-anion derivatives - of sulfonates chosen from mesylate or methanesulfonate (CH3SO2O), triflate or trifluoromethanesulfonate (CF3SO2O), - of borates chosen from BPh4, B(C6F5)4, or tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr14), - of perchlorate (C1O4).

13. A method according to any one of claims 1 to 12, characterized in that the concentration of supporting electrolyte is between 0.01 mol.11 and 5 mol.

11.

14. A process according to any one of claims 1 to 13, characterized in that the process is carried out at a constant potential between -0.5 V and -3 V (vs ferrocene or Fc0 / +).

15. Use of a process according to any one of claims 1 to 14, for the recycling of (pseudo-)halosilanes from the corresponding hydrosilanes.