Synthesis of Ruthenium Boryl Analogues of the Shvo Metal−Ligand Bifunctional Catalyst

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• 作者：Liza Koren-Selfridge ; Ian P. Query ; Joel A. Hanson ; Nicholas A. Isley ; Ilia A. Guzei ; Timothy B. Clark
• 刊名：Organometallics
• 出版年：2010
• 出版时间：September 13, 2010
• 年：2010
• 卷：29
• 期：17
• 页码：3896-3900
• 全文大小：826K
• 年卷期：v.29,no.17(September 13, 2010)
• ISSN：1520-6041

文摘

Metal boryl complexes have received significant attention in the literature in recent years due to their role as key intermediates in a number of metal-catalyzed borylation reactions. The ligand scaffold is known to have a significant impact on the observed reactivity of these metal boryl complexes. A synthetic strategy to access ruthenium boryl analogues of the Shvo metal−ligand catalysts is described. Heating a precursor to Shvo’s catalyst (1) with bis(catecholato)diboron at 50 °C provided ruthenium boryl complex 3, [2,5-Ph₂-3,4-Tol₂(η⁵-C₄COBcat)Ru(CO)₂Bcat] (Bcat = catecholatoboryl). Addition of bis(catecholato)diboron to complex 1 in the presence of a phenol results in ruthenium boryl complex 5, [2,5-Ph₂-3,4-Tol₂(η⁵-C₄COH)Ru(CO)₂Bcat], at 22 °C in 30% isolated yield. A single-crystal X-ray analysis of complex 5 confirmed the assigned structure. An improved synthesis of ruthenium boryl complex 5 was developed by the in situ formation of complex 3, [2,5-Ph₂-3,4-Tol₂(η⁵-C₄COBcat)Ru(CO)₂Bcat], followed by addition of the phenol, resulting in a 51% yield.