title: Influence of the metal orbital occupancy and principal quantum number on organoazide (RN3) conversion to transition-metal imide complexes.
abstract: The reaction of phenyl azide with (PNP)Ni, where PNP = ( (t)Bu 2PCH 2SiMe 2) 2N (-), promptly evolves N 2 and forms a P=N bond in the product (PNP=NPh)Ni (I). A similar reaction with (PNP)FeCl proceeds to form a P=N bond but without N 2 evolution, to furnish (PNP=N-N=NPh)FeCl. An analogous reaction with (PNP)RuCl occurs with a more dramatic redox change at the metal (and N 2 evolution), to give the salt composed of (PNP)Ru(NPh) (+) and (PNP)RuCl 3 (-), together with equimolar (PNP)Ru(NPh). The contrast among these results is used to deduce what conditions favor N 2 loss and oxidative incorporation of the NPh fragment from PhN 3 into a metal complex.
authors.affiliation: Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: Amy N
authors.initials: AN
authors.lastname: Walstrom
authors.forename: Benjamin C
authors.initials: BC
authors.lastname: Fullmer
authors.forename: Hongjun
authors.initials: H
authors.lastname: Fan
authors.forename: Maren
authors.initials: M
authors.lastname: Pink
authors.forename: Drew T
authors.initials: DT
authors.lastname: Buschhorn
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton