title: A computational study of metal-mediated decomposition of nitrene transfer reagents.
abstract: Metal-mediated decomposition to form nitrene complexes is investigated by using DFT for prototypical organic azides and iodonium imides used in organic synthesis. Each system exhibited exothermic pathways via formation of cyclic intermediates, which decompose to yield LNi = NX + Y (L = bis-phosphine, NX = nitrene, Y = N2 or IPh). Also, the typical heterotransfer reagents used in organic synthesis show a greater tendency toward triplet nitrene complexes and hence the potential for metal-free reactivity than aliphatic and aromatic substituted versions.
authors.affiliation: Department of Chemistry for Advanced Scientific Computing and Modeling, University of North Texas, P.O. Box 305070, Denton, Texas 76203-5070, USA. t@unt.edu
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari
authors.forename: Glenn R
authors.initials: GR
authors.lastname: Morello