Heterolytic Cleavage of Dihydrogen by an Iron(II) PNP Pincer Complex via Metal-Ligand Cooperation.

ABSTRACT: The bis-carbonyl Fe(II) complex trans-[Fe(PNP-iPr)(CO)₂Cl]⁺ reacts with Zn as reducing agent under a dihydrogen atmosphere to give the Fe(II) hydride complex cis-[Fe(PNP-iPr)(CO)₂H]⁺ in 97% isolated yield. A crucial step in this reaction seems to be the reduction of the acidic NH protons of the PNP-iPr ligand to afford H₂ and the coordinatively unsaturated intermediate [Fe(PNP^H-iPr)(CO)₂]⁺ bearing a dearomatized pyridine moiety. This species is able to bind and heterolytically cleave H₂ to give cis-[Fe(PNP-iPr)(CO)₂H]⁺. The mechanism of this reaction has been studied by DFT calculations. The proposed mechanism was s

SUBMITTER: Bichler B 

PROVIDER: S-EPMC3751463 | biostudies-literature | 2013 Aug

REPOSITORIES: biostudies-literature