239076-81-4Relevant articles and documents
A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour
Dunne, John P.,Blazina, Damir,Aiken, Stuart,Carteret, Hilary A.,Duckett, Simon B.,Jones, Jonathan A.,Poli, Rinaldo,Whitwood, Adrian C.
, p. 3616 - 3628 (2007/10/03)
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.
PHOTOCHEMICAL HYDROFORMYLATION CATALYSIS USING RUTHENIUM COMPLEXES
Gordon, Edward M.,Eisenberg, Richard
, p. C53 - C57 (2007/10/02)
The catalytic hydroformylation of ethylene and propylene is promoted photochemically by the ruthenium(0) complexes Ru(CO)3(PPh3)2, Ru(CO)4(PPh3) and Ru3(CO)12 under UV irradiation at low pressure (ca. 500 torr H2/CO, 1/1) and ambient temperature.Subsequent hydrogenation of the aldehydes is also observed.The photolyses are performed in benzene solution and result in competitive hydroformylation and hydrogenation of the olefin to yield a product mixture of alkane, aldehydes and alcohols.The use of 13CO shows that the ligands in Ru(CO)3(PPh3)2 exchange readily under photolysis, and that under catalytic conditions Ru(CO)3(PPh3)2 is slowly converted to Ru(CO)4(PPh3) as the only observable Ru species in solution.Incorporation of 13C into the carbonyl position of propanal and the C(1) position of 1-propanol is observed directly by NMR spectroscopy.The tetracarbonyl complex exchanges CO readily at ambient temperature, and upon irradiation under H2 forms the unstable dihydride complex RuH2(CO)3(PPh3).A mechanism is proposed for the observed hydroformylation in which the photochemical step is thought to be generation of a coordinatively unsaturated Ru species.
