| Budget Amount *help |
¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 1999: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1998: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Research Abstract |
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.
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