iPr2N–P═Fe(CO)4 in Olefinic Solvents: A Reservoir of a Transient Phosphinidene Complex Capable of Substrate Hopping

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• 作者：Jan B. M. Wit ; G. Bas de Jong ; Marius Schakel ; Martin Lutz ; Andreas W. Ehlers ; J. Chris Slootweg ; Koop Lammertsma
• 刊名：Organometallics
• 出版年：2016
• 出版时间：April 25, 2016
• 年：2016
• 卷：35
• 期：8
• 页码：1170-1176
• 全文大小：400K
• 年卷期：0
• ISSN：1520-6041

文摘

The phosphinidene complex iPr₂N–P═Fe(CO)₄ was prepared as a storable phosphirane solution from Collman’s reagent and iPr₂NPCl₂ in the olefins 1-pentene and 1-hexene. The carbene-like reagent is able to hop under very mild conditions (>−25 °C) from one olefin to another and to alkynes to give the more stable phosphirenes that likewise display dynamic covalent behavior. The olefinic solutions are effective reservoirs for the highly reactive phosphinidene complex, as is illustrated in its N–H and O–H insertion reactions with amines, alcohols, and carboxylic acids and in its P–C bond formation with Grignard reagents.