Reactivity of the triruthenium ortho

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• 作者：Shishir Ghosh ; Shahed Rana ; Derek A. Tocher ; Graeme Hogarth ; Ebbe Nordl ; er ; Shariff E. Kabir
• 关键词：Diphosphines ; Triruthenium ; Carbonyl ; Tri(2-thienyl)phosphine ; Tri(2-furyl)phosphine ; X-ray structures
• 刊名：Journal of Organometallic Chemistry
• 出版年：2009
• 出版时间：15 September 2009
• 年：2009
• 卷：694
• 期：20
• 页码：3312-3319
• 全文大小：645 K

文摘

Reaction of [Ru₃(CO)₉{μ₃-η¹,κ¹,κ²-PhP(C₆H₄)CH₂PPh}] (1) with tri(2-thienyl)phosphine (PTh₃) in refluxing THF afforded [Ru₃(CO)₉(PTh₃)(μ-dpbm)] (3) {dpbm = PhP(C₆H₄)(CH₂)PPh} and [Ru₃(CO)₆(μ-CO)₂{μ-κ¹,η¹-PTh₂(C₄H₂S)}{μ₃-κ¹,κ²-Ph₂PCH₂PPh}] (5) in 18 % and 12 % yields, respectively, while a similar reaction with tri(2-furyl)phosphine (PFu₃) gave [Ru₃(CO)₉(PFu₃)(μ-dpbm)] (4) and [Ru₃(CO)₇(μ-η¹,η²-C₄H₃O)(μ-PFu₂){μ₃-η¹,κ¹,κ²-PhP(C₆H₄)CH₂PPh}] (6) in 24 % and 27 % yields, respectively. Compounds 2 and 4 are phosphine adducts of 1 in which the diphosphine ligand is transformed into 1,3-diphenyl-2,3-dihydro-1H-1,3-benzodiphosphine (dpbm) via phosphorus–carbon bond formation. Cluster 5 results from metalation of a thienyl ring, the cleaved proton being transferred to the diphosphine. Carbon–phosphorus bond cleavage of a PFu₃ ligand is observed in 6 to afford a phosphido-bridge and a furyl fragment, the latter bridging in a σ,π-vinyl fashion. The molecular structures of 3, 5 and 6 have been determined by X-ray diffraction studies.