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

我找到了一个Dinuclear Iry D1 I D1复合体[IrCl]（diphosphane）D22即使携带perarylphosphanes which are not so强的电子捐赠{diphosphane=2，2'-bis（二苯磷酰胺）-1，1 '-binapthyl（BINAP）或双（diphenylphosphino）-1，1'-biphenyl（BPBP）} can easily activate protic molecules {MeOH， H-D22-D2O， RCO-D22-D2H（R=Me， Ph）， PhSH} at ambient temperature。[{Ir{（R）-binap}（H）（μ-OMe）} D22-D2（μ-Cl）] Cl. MeOH通过X射线分析、光谱数据和元素分析确认。[IrCl（diphophane）]碘D22碘D2和protic molecules{H碘D22碘D2 O， RCO碘D22碘D2 H（R=Me， Ph）， PhSH} gave hydrido（hydroxo）-， hydrido（carboxylato）-， and hydido（thilato）-复杂，负责任。这些复合体也被认为是通过核磁共振光谱数据、元素分析和限制平等条件来实现的模拟核结构。The complex [IrCl（diphosphane）]イイD22イエD2 easily reacted with two equivalents of neutral ligands{PPHイD23イエD2， PCyイD23イエD2， P（OPH）イD23イエD2}at ambient temperature to give the corresponding mononuclear complexes in good y\。I have found that the mononuclear complexes react with molecular hydrogen or methanol to give the dihydrido-iridium complex IrCl（H）イD22イエD2（diphosphane）（L）（L=PPhイD23イエD2， PCyイD23イエD2）。I have found that hydrido（methoxo） complexes serve as efficient catalyst precursors for reduction of internal alkynes to give trans-ales using methanol as a source of hydrogen。氢化物（羧化）-乙二胺（III）复合物被发现可用于甲苯或甲苯/MeOH（MeOH）中的非对称氢化前胺的活性;氢化物（羟基）-乙二胺（III）复合物被发现可用于硝酸盐（乙腈或苯并腈）的氢化物。我正在研究催化剂氢化的最佳化。

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.