| 19153632 |
Gutsulyak DV, Osipov AL, Kuzmina LG, Howard JA, Nikonov GI: Unexpected effect of the ring on the extent of Si..H interligand interactions in half-sandwich silyl hydrides of ruthenium.. Dalton Trans. 2008 Dec 21;(47):6843-50. Epub 2008 Oct 14.
This paper reports preparation of new silyl hydride complexes of ruthenium supported by the Cp/PR (3) ligand set. It is shown that the easiest and most general route to these complexes is provided by the thermal reaction of [RuCp (PR (3))(H)(3)] with hydrosilanes. Complexes [RuCp (PR (3))(H)(2)(SiMe (2) Cl)] exhibit Interligand Hypervalent Interactions (IHI) between the hydride and silyl ligands. Comparison of the X-ray structures of complexes [RuCp (PPr (i)(3))(H)(2)(SiMe (2) Cl)], [RuCp (PPhPr (i)(2))(H)(2)(SiMe (2) Cl)], and [RuCp (PPh (3))(H)(2)(SiMe (2) Cl)] shows that the IHI weakens with the decreasing electron-releasing ability of the phosphine. Comparison of the X-ray structure of [RuCp (PPh (3))(H)(2)(SiMe (2) Cl)] with the structure of the previously reported complex [RuCp*(PPh (3))(H)(2)(SiMe (2) Cl)] reveals that the lack of IHI in the latter compound is due to unfavourable steric interactions between the bulkier Cp* ring and the SiMe (2) Cl group. |
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