Hydrogen bonds, coordination isomerism, and catalytic dehydrogenation of alcohols with the bifunctional iridium pincer complex (HOCH2)2(PCsp3P) IrHCl

G. A. Silantyev, E. M. Titova, O. A. Filippov, E. I. Gutsul, D. Gelman, N. V. Belkova*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The reaction of iridium(iii) hydride complex 1 based on the pincer dibenzobarrelene ligand (HOCH2)2(PCsp3P) with pyridine proceeds stepwise to show different reactivities of the starting fac-isomers 1A and 1B. The kinetic product of the reaction is mer-complex 2 with a trans disposition of the pyridine and hydride ligands. Isomerization into the thermodynamic product 2′ containing pyridine in the cis-position with regard to hydride proceeds slowly. The estimation of activation parameters (ΔH and ΔS) shows that the change in the geometry of fac-complexes upon coordination of pyridine occurs through an associative transition state, while isomerization of the mer-complexes is a dissociative process. The isomers of complex 1 and its pyridine-containing derivatives 2 and 2′ are shown to exhibit different reactivities in the formation of dihydrogen bond and the catalytic dehydrogenation of PriOH under model conditions.

Original languageAmerican English
Pages (from-to)2806-2810
Number of pages5
JournalRussian Chemical Bulletin
Volume64
Issue number12
DOIs
StatePublished - 1 Dec 2015

Bibliographical note

Publisher Copyright:
© 2015, Springer Science+Business Media New York.

Keywords

  • IR spectroscopy
  • NMR spectroscopy
  • hydrogen bonds
  • transition metal hydrides

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