Metal-ligand cooperation in the trans addition of dihydrogen to a pincer Ir(i) complex: A DFT study

Mark A. Iron, Eyal Ben-Ari, Revital Cohen, David Milstein

Research output: Contribution to journalArticle

90 Citations (Scopus)


DFT calculations on the hydrogenation of a (PNP)Ir(i) complex, to give the trans - rather then the cis - dihydride isomer, show that the reaction proceeds via a deprotonation/protonation of the ligand arm with concomitant dearomatization/aromatization of the pyridine core. Thus, the actual H 2 activation step occurs by an Ir(iii) complex and not by the Ir(i) starting complex, as supported by experimental observations. This ligand participation allows for products that would otherwise be inaccessible. In addition, trace amounts of water, which are likely to be present in the solvent, facilitate proton transfer reaction steps.

Original languageEnglish
Pages (from-to)9433-9439
Number of pages7
JournalDalton Transactions
Issue number43
Publication statusPublished - Nov 2 2009


ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this