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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Oxidative addition of silanes R_3SiH to the unsaturated cluster[Os_3(mu-H){mu_3-PH_2PCH_2PPh(C_6H_4)}(CO)_8]:Evidence for reversible silane formation in the dynamic behaviour of[Os_3(mu-H)-(SiR_3)(CO)_9(mu-dppm)]
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Oxidative addition of silanes R_3SiH to the unsaturated cluster[Os_3(mu-H){mu_3-PH_2PCH_2PPh(C_6H_4)}(CO)_8]:Evidence for reversible silane formation in the dynamic behaviour of[Os_3(mu-H)-(SiR_3)(CO)_9(mu-dppm)]

机译：硅烷R_3SiH氧化加成到不饱和簇[Os_3（mu-H）{mu_3-PH_2PCH_2PPh（C_6H_4）}（CO）_8]：[Os_3（mu-H）-（SiR_3）动力学行为中可逆硅烷形成的证据）（CO）_9（mu-dppm）]

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摘要

Oxidative addition of the silanes R_3SiH(R_3 = PH_3,Et_3,EtME_2)to the unsaturated cluster[Os_3(mu-H){mu_3-PH_2PCH_2PPh(C_6H_4)}(CO)_8]leads to the saturated clusters[Os_3(mu-H)(SiR_3)(CO)_9(mu-dppm)](SiR_3-SiPH_31,SiEt_3 2 and SiEtME_2 3)and the unsaturated clusters[Os_3(mu-H)_2(SiR_3){mu_3-PH_2PCH_2PPh(C_6H_4)}(CO)7](SiR_3 = SiPH_3 4,SiEt_3 5 and SiEtME_2 6).Structures are based on spectroscopic evidence and a XRD structure of[Os_3(mu-H)(SiPH_3)(CO)_9(mu-dppm)]1 in which all non-CO ligands are coordinated equatorially and the hydride and the silyl groups are mutually cis.From variable-temperature ~1H NMR spectra of the SiEt_3 compound 2,exchange of the P nuclei is clearly apparent.Simultaneous migrations of the SiEt_3 group and of the hydride from one Os-Os edge to another generate a time-averaged mirror plane in the molecule.VT !H NMR spectra of the somewhat less bulky compound[Os_3(eta-H)(SiME_2Et)(CO)_9(mu-dppm)]3 have been analysed.Two isomers 3a and 3b are observed with the hydride ligand located on different Os-Os edges.Synchronous migration of the hydride and SiME_2Et groups is faster than the observed interconversion of isomers which occurs by hydride migration alone.The synchronous motion of H and SiR_3 only occurs when these ligands are mutually cis as in the major isomer 3a and we propose that this process requires the formation of a transient silane complex of the type[Os_3(eta~2-HSiR_3)(CO)_9(mu-dppm)].Turnstile rotation within an Os(CO)_3(eta~2-HSiR_3)group leads to the observed exchange within the major isomer 3a without exchange with the minor isomer.This process is not observed for the minor isomer 3b because the hydride and the silyl group are mutually trans.Protonation to give[Os_3(eta-H)_2(SiR_3)(CO)_9(eta-dppm)]~+ totally suppresses the dynamic behaviour because there are no edge vacancies.
机译：硅烷R_3SiH（R_3 = PH_3，Et_3，EtME_2）的氧化加成到不饱和簇[Os_3（mu-H）{mu_3-PH_2PCH_2PPh（C_6H_4）}（CO）_8]导致饱和簇[Os_3（mu-H） ）（SiR_3）（CO）_9（mu-dppm）]（SiR_3-SiPH_31，SiEt_3 2和SiEtME_2 3）和不饱和簇[Os_3（mu-H）_2（SiR_3）{mu_3-PH_2PCH_2PPh（C_6H_4）}（CO ）7]（SiR_3 = SiPH_3 4，SiEt_3 5和SiEtME_2 6）。结构基于光谱证据和[Os_3（mu-H）（SiPH_3）（CO）_9（mu-dppm）] 1的XRD结构从SiEt_3化合物2的〜1H NMR变温谱图可以清楚地看出P核的交换。SiEt_3基团和硅藻土的同时迁移。氢化物从一个Os-Os边缘到另一个边缘会在分子中生成一个时均镜面。体积稍小的化合物[Os_3（eta-H）（SiME_2Et）（CO）_9（mu-dppm）的VT！H NMR光谱）] 3的分析。观察到两个异构体3a和3b与水阴离子配体位于不同的Os-Os边缘。氢化物和SiME_2Et基团的同步迁移比观察到的仅由氢化物迁移引起的异构体的相互转化快.H和SiR_3的同步运动仅在这些配体互为顺式时发生主要异构体3a，我们建议此过程需要形成类型为[Os_3（eta〜2-HSiR_3）（CO）_9（mu-dppm）]的瞬态硅烷配合物。Os（CO）_3内的旋转旋转（eta〜2-HSiR_3）基团导致在主要异构体3a内观察到交换而未与次要异构体交换。对于次要异构体3b未观察到此过程，因为氢化物和甲硅烷基是相互反式的。 Os_3（η-H）_2（SiR_3）（CO）_9（η-dppm）] ++由于没有边缘空位，因此完全抑制了动态行为。

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