Preparation and reactivity of germyl complexes of ruthenium and osmium stabilised by cyclopentadienyl, indenyl and tris(pyrazolyl)borate fragments

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• 作者：Gabriele Albertin ; Stefano Antoniutti ; Jes煤s Castro ; Federica Scapinello
• 关键词：Synthesis ; Trihydridogermyl and triethoxygermyl ; Half-sandwich complexes ; Ruthenium and osmium ; Tris(pyrazolyl)borate ligand
• 刊名：Journal of Organometallic Chemistry
• 出版年：1 February, 2014
• 年：2014
• 卷：751
• 期：Complete
• 页码：412-419
• 全文大小：610 K

文摘

Half-sandwich trichlorogermyl complexes Ru(GeCl₃)(畏⁵-C₅H₅)(PPh₃)L (1) and Ru(GeCl₃)(畏⁵-C₉H₇)(PPh₃)L (2) [L聽=聽P(OMe)₃ (a), P(OEt)₃ (b) and PPh(OEt)₂ (c)] were prepared by allowing chloro compounds RuCl(畏⁵-C₅H₅)(PPh₃)L and RuCl(畏⁵-C₉H₇)(PPh₃)L to react with an excess of GeCl₂路dioxane in ethanol. Treatment of trichlorogermyl complexes 1 and 2 with LiAlH₄ in THF yielded trihydridogermyl derivatives Ru(GeH₃)(畏⁵-C₅H₅)(PPh₃)L (3) and Ru(GeH₃)(畏⁵-C₉H₇)(PPh₃)L (4). Instead, reaction of trichlorogermyl complexes 1 and 2 with NaBH₄ in ethanol afforded triethoxygermyl complexes Ru[Ge(OEt)₃](畏⁵-C₅H₅)(PPh₃)L (5) and Ru[Ge(OEt)₃](畏⁵-C₉H₇)(PPh₃)L (6). Trichlorogermyl complexes with the tris(pyrazolyl)borate ligand M(GeCl₃)(Tp)(PPh₃)L [M聽=聽Ru (7), Os (10)] were prepared by reacting chloro compounds MCl(Tp)(PPh₃)L with an excess of GeCl₂路dioxane. Depending on metal centre, nature of phosphite and experimental conditions, the reaction of trichlorogermyl complexes 7 and 10 with LiAlH₄ or NaBH₄ afforded trihydridogermyl M(GeH₃)(Tp)(PPh₃)L (8, 12) and triethoxygermyl derivatives M[Ge(OEt)₃](Tp)(PPh₃)L (9, 11). The complexes were characterised by IR and multinuclear NMR spectroscopy and by X-ray crystal structure determination of 3a.