A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour

John P. Dunne, Damir Blazina, Stuart Aiken, Hilary A. Carteret, Simon B. Duckett, Jonathan A. Jones, Rinaldo Poli, Adrian C. Whitwood

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)


The photochemical reaction of Ru(CO)3(L)2, where L = PPh3, PMe3, PCy3 and P(p-tolyl)3 with parahydrogen (p-H2) 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 and 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 H2 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 π-accepting OC-Ru-CO axis.

Original languageEnglish
Pages (from-to)3616-3628
Number of pages13
JournalDalton Transactions
Issue number21
Early online date16 Sep 2004
Publication statusPublished - 7 Nov 2004
Externally publishedYes


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