Facile Activation of Protic Molecules by Ir (I) and Rh (I) Complexes and Their Application

I have found that dinuclear IrⅡD1IⅡD1 complexes[IrCl(Diphosphane)]ⅡD22ⅡD2 carrying even perarylphospanes which are not so strong electron donting{diphosphane=2，2‘-bis(Diphenylphosphino)-1，1’-binapthyl(BINAP)or bis(Diphenylphosphino)-1，1‘-biphenyl(BPBP)}can easily activate protic molecules{MeOH，H i D22D2O，Rami D_2}The concrete structure of[{Ir{(R)-binap}(H)(µ-OMe)}I D 22 I D 2(µ-Cl)]Cl.MeOH has confirmed by X-ray analysis，spectaral data，and elemental analysis.The reactions of[IrCl(Diphophane)]I D 22个D 2 and protic molecules{H I D 22个D 2O，RCO I D 22个D 2 H(R=Me，Ph)，PhSH}gave hydrido(Hydroxo)-，hydrido(Carboxylato)-，and hydido(Thilato)-complexes，respectively。Those complexes are also considered to takeanalogous dinuclear structures by NMR spectal data，elemental analyses，and limiting equivalent conductances.The complex[IrCl(Diphosphane)]I D 22 I D 2 easily reacted with two equivalents of neutral ligands{PPh I D 23 I D 2，PCy I D 23 I D 2，P(OPh)I D 23 I D 2}at ambient temperature to give the corresponding mononuclear complexes in good yield.I have found that the mononuclear complexes react with molecular hydrogen or methanol to give the dihydrido-iridium complex IrCl(H)I D 22 I e D2(Diphosphane)(L)(L=PPh I D 23个D 2，PCy I D 23个D 2).I have found that hydrido(Methoxo)complexes serve as efficient catalyst precursors for reduction of internal alkynes to give trans-alkenes using methanol as a source of hydrogen.Overhydrogenation to alkanes was also accompanied.The hydrido(Carboxylato)-iridium(III)complex was found to be active for asymmetric hydrogenation of prochiral imines in toluene or toluene/MeOH to optically active amines.The hydrido(Hydroxo)-iridium(III)complex was found to be active for hydration of nitriles(Acetonitrile Or Benzonitrile)。I am examining the optimization of catalytic hydration。

I have found that dinuclear IrィイD1IィエD1 complexes [IrCl(diphosphane)]ィイD22ィエD2 carrying even perarylphospanes which are not so strong electron donting {diphosphane=2,2'-bis(diphenylphosphino)-1,1'-binapthyl (BINAP) or bis(diphenylphosphino)-1,1'-biphenyl(BPBP)} can easily activate protic molecules {MeOH, HィイD22ィエD2O, RCOィイD22ィエD2H(R=Me, Ph), PhSH} at ambient temperature. The concrete structure of [{Ir{(R)-binap}(H)(μ-OMe)}ィイD22ィエD2(μ-Cl)] Cl.MeOH has confirmed by X-ray analysis, spectaral data, and elemental analysis. The reactions of [IrCl(diphophane)]ィイD22ィエD2 and protic molecules{HィイD22ィエD2O, RCOィイD22ィエD2H(R=Me, Ph), PhSH} gave hydrido(hydroxo)-, hydrido(carboxylato)-, and hydido(thilato)-complexes, respectively. Those complexes are also considered to takeanalogous dinuclear structures by NMR spectal data, elemental analyses, and limiting equivalent conductances. The complex [IrCl(diphosphane)]ィイD22ィエD2 easily reacted with two equivalents of neutral ligands{PPhィイD23ィエD2, PCyィイD23ィエD2, P(OPh)ィイD23ィエD2}at ambient temperature to give the corresponding mononuclear complexes in good yield. I have found that the mononuclear complexes react with molecular hydrogen or methanol to give the dihydrido-iridium complex IrCl(H)ィイD22ィエD2(diphosphane)(L)(L=PPhィイD23ィエD2, PCyィイD23ィエD2).I have found that hydrido(methoxo) complexes serve as efficient catalyst precursors for reduction of internal alkynes to give trans-alkenes using methanol as a source of hydrogen. Overhydrogenation to alkanes was also accompanied.The hydrido(carboxylato)-iridium(III) complex was found to be active for asymmetric hydrogenation of prochiral imines in toluene or toluene/MeOH to optically active amines.The hydrido(hydroxo)-iridium(III) complex was found to be active for hydration of nitriles (acetonitrile or benzonitrile). I am examining the optimization of catalytic hydration.