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

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Abstract

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 H2 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
JournalJournal of the Chemical Society. Dalton Transactions
Issue number43
DOIs
Publication statusPublished - Oct 26 2009

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Discrete Fourier transforms
Ligands
Aromatization
Deprotonation
Proton transfer
Protonation
Isomers
Hydrogenation
Chemical activation
Water
pyridine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Metal–ligand cooperation in the trans addition of dihydrogen to a pincer Ir(i) complex : A DFT study. / Iron, Mark A.; Ben-Ari, Eyal; Cohen, Revital; Milstein, David.

In: Journal of the Chemical Society. Dalton Transactions, No. 43, 26.10.2009, p. 9433-9439.

Research output: Contribution to journalArticle

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