Reactivity of ˙NO with an osmium polyhydride: Reductive elimination and reductive nitrosylation on the path from odd- to even-electron molecules†
Abstract
The reaction of ˙NO with (PNP)Os(H)3, where PNP is N(SiMe2CH2PtBu2)2, involves H2 loss from a 1 : 1 adduct to form the intermediate (PNP)OsH(NO)2, which then forms coordinated HNO; loss of this triatomic molecule forms the final metal complex product in high yield: (PNP)Os(NO). Under a different concentration of gaseous reagents, a second path leads to the same products. These results are supported by spectroscopic observations at various temperatures, as well as by DFT calculations of the energies of alternative transition states and intermediates.