title: O/C bond cleavage of CO2 by NiI.
abstract: Reaction of (PNP)Ni, where PNP is [((t)Bu2PCH2SiMe2)2N](-1), with CO2 occurs rapidly even at -60 degrees C to form exclusively the product of transposition of the amide N and one CO2 oxygen: [((t)Bu2PCH2SiMe2)2O]Ni(NCO). DFT(B3LYP) evaluation of several candidate intermediates for breaking two Si/N and one C/O bond and forming two Si/O and one N/C bond reveal species at and below the energy of the separated particles, and establish the location of the spin densities in each.
authors.affiliation: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
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: Kenneth G
authors.initials: KG
authors.lastname: Caulton