title: Well-defined vanadium organoazide complexes and their conversion to terminal vanadium imides: structural snapshots and evidence for a nitrene capture mechanism.
abstract: 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.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: W Hill
authors.initials: WH
authors.lastname: Harman
authors.forename: Michael F
authors.initials: MF
authors.lastname: Lichterman
authors.forename: Nicholas A
authors.initials: NA
authors.lastname: Piro
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Chang
mesh_terms: D001386:Azides / Q000737:chemistry*; D007094:Imides / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014639:Vanadium / Q000737:chemistry*
chemical_list: D001386:Azides; D007094:Imides; D007097:Imines; D009942:Organometallic Compounds; D014639:Vanadium; C017621:phenylnitrene