Reactions of [Cp2M(SH)2] (M = Mo 1, W 2) with one equiv of [IrH2(PPh3)2(Me2CO)2][PF6] in acetone at room temperature under 1 atm of H2 afforded the hydrosulfido–hydrido complexes [Cp2M(μ-SH)2IrH2(PPh3)2][PF6] (M = Mo 4, W 5), whereas those of 1 and 2 with [RhH2(PPh3)2(Me2CO)(EtOH)][PF6] 6 resulted in the formation of [Cp2Mo(μ-SH)2Rh(PPh3)2][PF6] 7 and
[Cp2W(μ-S)2Rh(PPh3)2][PF6] 8. X-Ray analyses have been undertaken to clarify the detailed structure of [Cp2Mo(μ-SH)2IrH2(PPh3)2][BPh4] derived from 4 along with 7 and 8. Bimetallic complexes 4, 5, 7, and 8 catalysed the hydrogenation of alkynes such as 1-octyne and tert-butyl propiolate at room temperature under 1 atm of H2, yielding 1-octene and tert-butyl acrylate as the major products, respectively. In both reactions, the Mo–Rh complex 7 showed the highest
catalytic activity, although even the reactions using 7 are much slower than those catalyzed by the mononuclear Rh complex 6.
室温下,在 1 个大气压的 H2 条件下,[Cp2M(SH)2](M = Mo 1,W 2)与等当量的[IrH2(PPh3)2(Me2CO)2][PF6]在
丙酮中发生反应,生成了氢
硫氢配合物[Cp2M(μ-SH)2IrH2(PPh3)2][PF6](M = Mo 4,W 5)、W 5),而 1 和 2 与 [RhH2(PPh3)2(Me2CO)(EtOH)][PF6] 6 生成 [Cp2Mo(μ-SH)2Rh(PPh3)2][PF6] 7 和 [Cp2W(μ-S)2Rh(PPh3)2][PF6] 8。通过 X 射线分析,阐明了由 4 以及 7 和 8 生成的[Cp2Mo(μ-SH)2IrH2(PPh3)2][BPh4]的详细结构。双
金属配合物 4、5、7 和 8 可在室温、1 atm 的 H2 下催化
1-辛炔和
丙炔酸叔丁酯等
炔烃的氢化反应,主要产物分别为 1-
辛烯和
丙烯酸叔丁酯。在这两个反应中,Mo-Rh 复合物 7 显示出最高的催化活性,尽管使用 7 的反应也比单核 Rh 复合物 6 催化的反应慢得多。