O/C bond cleavage of CO2 by NiI.
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.
Fullmer
Benjamin C
BC
Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
Fan
Hongjun
H
Pink
Maren
M
Caulton
Kenneth G
KG