title: Mechanism of N/O bond scission of N2O by an unsaturated rhodium transient.
abstract: The mechanism of formation of triplet (PNP)RhO and (PNP)Rh(N(2)) (PNP = N(SiMe(2)CH(2)P(t)Bu(2))(2)) from reaction of two molecules of (PNP)Rh with N(2)O has been studied by DFT, evaluating mechanisms which (1) involve free N(2), and (2) which effect N/O bond scission in linearly coordinated (PNP)RhNNO. This work shows the variety of modes of binding N(2)O to this reducing, unsaturated metal fragment and also evaluates why a mechanism avoiding free N(2) is preferred. Comparisons are made to isoelectronic CO(2) in its reaction with (PNP)Rh.
authors.affiliation: Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
authors.forename: José G
authors.initials: JG
authors.lastname: Andino
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton