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From the same journal

A combined parahydrogen and theoretical study of H-2 activation by 16-electron d(8) ruthenium(0) complexes and their subsequent catalytic behaviour

Research output: Contribution to journalArticle

Published copy (DOI)

Author(s)

  • J P Dunne
  • D Blazina
  • S Aiken
  • H A Carteret
  • S B Duckett
  • J A Jones
  • R Poli
  • A C Whitwood

Department/unit(s)

Publication details

JournalDalton Transactions
DatePublished - 2004
Issue number21
Number of pages13
Pages (from-to)3616-3628
Original languageEnglish

Abstract

The photochemical reaction of Ru(CO)(3)(L)(2), where L = PPh3, PMe3, PCy3 and P(p-tolyl)(3) with parahydrogen (p-H-2) has been studied by in-situ NMR spectroscopy and shown to result in two competing processes. The first of these involves loss of CO and results in the formation of the cis-cis-trans-L isomer of Ru(CO)(2)(L)(2)(H)(2), while in the second, a single photon induces loss of both CO and L and leads to the formation of cis-cis-cis Ru(CO)(2)(L)(2)(H)(2) Ru(CO)(2)(L)(solvent)(H)(2) where solvent = toluene, THF and pyridine (py). In the case of L = PPh3, cis-cis-trans-L Ru(CO)(2)(L)(2)(H)(2) is shown to be an effective hydrogenation catalyst with rate limiting phosphine dissociation proceeding at a rate of 2.2 s(-1) in pyridine at 355 K. Theoretical calculations and experimental observations show that H-2 addition to the Ru(CO)(2)(L)(2) proceeds to form cis-cis-trans-L Ru(CO)(2)(L)(2)(H)(2) as the major product via addition over the pi-accepting OC-Ru-CO axis.

    Research areas

  • HYDROGEN INDUCED POLARIZATION, DIHYDRIDE COMPLEXES, NMR-SPECTROSCOPY, STRUCTURAL-CHARACTERIZATION, HOMOGENEOUS HYDROGENATION, CARBONYL-COMPLEXES, OXIDATIVE ADDITION, UNSATURATED RU(0), SPIN POLARIZATION, INORGANIC SYSTEMS

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