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

作者：Harman W Hill; Lichterman Michael F; Piro Nicholas A; Chang Christopher J^*

来源：Inorganic Chemistry, 2012, 51(18): 10037-10042.

DOI：10.1021/ic301673g

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.

• 出版日期2012-9-17