Synthesis and Reactivity of Ruthenium Arene Complexes Incorporating Novel Ph2PCH2CH2BR2 Ligands. Easy Access to the Four-Membered Ruthenacycle [(p-cy

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• 作者：Jé ; rô ; me Vergnaud ; Mary Grellier ; Ghenwa Bouhadir ; Laure Vendier ; Sylviane Sabo-Etienne ; Didier Bourissou
• 刊名：Organometallics
• 出版年：2008
• 出版时间：March 24, 2008
• 年：2008
• 卷：27
• 期：6
• 页码：1140 - 1146
• 全文大小：140K
• 年卷期：v.27,no.6(March 24, 2008)
• ISSN：1520-6041

文摘

The ambiphilic ligands Ph₂PCH₂CH₂BR₂ (1a,b: BR₂ = BCy₂ (a), 9-BBN (b)) were readily prepared by hydroboration of vinyldiphenylphosphine. Reaction of 1a,b with [(p-cymene)RuCl₂]₂ afforded the corresponding complexes [(p-cymene)RuCl₂(Ph₂PCH₂CH₂BR₂)] (2a,b), in which the borane moiety remains pendant, as confirmed by an X-ray diffraction analysis of 2b. Reaction of 2a,b with AgBF₄ in the presence of acetonitrile leads to the formation of the corresponding cationic complexes [(p-cymene)RuCl(Ph₂PCH₂CH₂BR₂)(CH₃CN)][BF₄] (3a,b) without alteration of the pendant borane moiety. In contrast, treatment of 2a,b with AgOAc induces CH₂−B bond cleavage and affords the four-membered ruthenacycle [(p-cymene)RuCl(κ^C,P-CH₂CH₂PPh₂)] (4), characterized by X-ray diffraction. By reaction with chlorodicyclohexylborane, 4 gives back 2a via ring-opening σ-bond metathesis, whereas 4 reacts with chlorodiethylalane via alkylation at ruthenium with retention of the four-membered metallacycle to afford the ethyl complex [(p-cymene)RuEt(κ^C,P-CH₂CH₂PPh₂)] (5).