Well-Defined Vanadium Organoazide Complexes and Their Conversion to Terminal Vanadium Imides: Structural Snapshots and Evidence for a Nitrene Capture Mechanism

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• 作者：W. Hill Harman ; Michael F. Lichterman ; Nicholas A. Piro ; Christopher J. Chang
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：September 17, 2012
• 年：2012
• 卷：51
• 期：18
• 页码：10037-10042
• 全文大小：279K
• 年卷期：v.51,no.18(September 17, 2012)
• ISSN：1520-510X

文摘

We report the synthesis and structural characterization of a family of well-defined organoazide complexes supported by a three-fold-symmetric pyrrolide scaffold and their conversion to the corresponding terminal imido congeners. Kinetic measurements on a series of structurally homologous but electronically distinct vanadium organoazide complexes reveal that the azido-to-imido transformations proceed via a process that is first-order in the metal complex and has a positive entropy of activation. Further studies suggest that these reactions may involve metal-mediated generation and capture of nitrene fragments.