Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

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• 作者：Lindsay T. Byrne ; Nicole S. Hondow ; George A. Koutsantonis ; Brian W. Skelton ; A. Asgar Torabi ; Allan H. White ; S. Bruce Wild
• 关键词：Ruthenium ; Cobalt ; Carbonyl substitution ; Cluster ; Thiol ; Secondary phosphine
• 刊名：Journal of Organometallic Chemistry
• 出版年：2008
• 出版时间：1 May 2008
• 年：2008
• 卷：693
• 期：10
• 页码：1738-1750
• 全文大小：447 K

文摘

The trimetallic clusters [Ru₃(CO)₁₀(dppm)], [Ru₃(CO)₁₂] and [RuCo₂(CO)₁₁] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH₂CH₂PHPh (ttp://www.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" title=""double bond; length as m-dash"" border=""0""> LH₂), gave two products under various conditions which have been characterised by spectroscopic and crystallographic means. These two complexes [Ru₃(μ-dppm)(H)(CO)₇(LH)] and [Ru₃(μ-dppm)(H)(CO)₈(LH)Ru₃(μ-dppm)(CO)₉], show the versatility of the ligand, with it chelating in the former and bridging two Ru₃ units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru₃(CO)₁₂] the reaction with LH₂ gave a poor yield of a tetranuclear butterfly cluster, [Ru₄(CO)₁₀(L)₂], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH₂CH₂AsMe(C₆H₄CH₂OMe), reacted with [RuCo₂(CO)₁₁] to give a low yield of the heterobimetallic Ru–Co adduct, [RuCo(CO)₆(SCH₂CH₂AsMe(C₆H₄CH₂OMe))], which appears to be the only one of its type so far structurally characterised.