Controlled cis Labilization of CO from Manganese(I) Mixed Carbonyl/Isocyanide Complexes: An Entry Point to Coordinatively Unsaturated Metallo-Lewis Acids

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• 作者：Douglas W. Agnew ; Curtis E. Moore ; Arnold L. Rheingold ; Joshua S. Figueroa
• 刊名：Organometallics
• 出版年：2017
• 出版时间：January 23, 2017
• 年：2017
• 卷：36
• 期：2
• 页码：363-371
• 全文大小：714K
• ISSN：1520-6041

文摘

Presented herein is a general design strategy for the formation of coordinatively unsaturated Mn(I) fragments via the cis labilization of CO using metal carboxylates and subsequent deprotection by a range of abstraction agents. A consistent trend is observed in the ability of carboxylate ligands to facilitate CO dissociation as a function of the electron-releasing properties of the carboxylate R group. This is in agreement with previous theoretical work on cis-labilizing ligands. A variety of κ²-coordinated carboxylates function as site-protection ligands for the [Mn(CO)₂(CNAr^Dipp2)₂]⁺ scaffold and can be liberated using a range of synthetic techniques. The coordinatively unsaturated species thus formed are shown to be strong metal-based Lewis acids and can engage in agostic-type interactions; in addition, they can be trapped as the corresponding solvento complexes by ethereal solvents.