Synthesis and Characterization of Pincer-Molybdenum Precatalysts for CO2 Hydrogenation

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• 作者：Yuanyuan Zhang ; Paul G. Williard ; Wesley H. Bernskoetter
• 刊名：Organometallics
• 出版年：2016
• 出版时间：March 28, 2016
• 年：2016
• 卷：35
• 期：6
• 页码：860-865
• 全文大小：375K
• ISSN：1520-6041

文摘

A family of low-valent molybdenum complexes supported by the pincer ligand PN^MeP (PN^MeP = MeN(CH₂CH₂PPh₂)₂) was prepared and characterized, including (PN^MeP)Mo(C₂H₄)₂, which contains an agostic interaction between the metal and the N-methyl substituent. This β-agostic C–H bond was cleaved by molybdenum and produced a cyclometalated molybdenum formate complex, (κ⁴-PN^MeP)Mo(C₂H₄)(κ²-O₂CH), upon exposure to CO₂. This species serves as a promotor of CO₂ hydrogenation to formate under basic conditions, a rare transformation for group VI metals. The performance of the precatalyst was enhanced with the addition of Lewis acid salts.