para-Hydrogen-induced polarization methods are shown to enable the in situ detection of linear and branched monophosphine-containing intermediates during hydroformylation when Co(eta3-C3H5)(CO)2(PCy3) is the catalyst precursor. The NMR signal characteristics of the alkyl arms of these species provide direct evidence for the rapid interconversion of linear and branched cobalt alkyls prior to the CO insertion step. The observation of additional para-hydrogen-enhanced signals for the corresponding linear and branched aldehydes enables the reactions selectivity to be rapidly monitored as a function of H2 and CO pressure or reaction temperature.

The selective dimerisation of the alpha-olefins 1-pentene through to 1-nonene is reported using an in situ-generated catalyst derived from tungsten hexachloride, aniline, triethylamine and alkylaluminium halide. The influence of reagent identity and reaction stoichiometry, along with activator, solvent and alpha-olefin substrate choice are probed. The catalyst is found to be highly selective towards dimerisation, minimising the formation of undesired heavier oligomers. Notably, the selectivity within the dimer fraction is found to favour the formation of products with methyl branches. The selectivity towards individual olefin isomers has been determined and the system is found to also produce trace levels of dienes and alkanes. A kinetic study of the system reveals a second order dependence on substrate. Comparison of the products observed, with those expected for metallacyclic and Cossee-type mechanisms, suggests that the latter is in operation, something confirmed by the results of a C(2)H(4)/C(2)D(4) co-dimerisation experiment which showed full isotopic scrambling in the products. Thus a mechanistic proposal is made to account for the observed behaviour of the system, including the diene and alkane formation.

NMR studies on the reaction of Ir(CO)(PPh(3))(2)(eta(3)-C(3)H(5)) with para-H(2) and CO enable the complete mapping of the hydroformylation mechanism for an iridium monohydride catalyst via the detection of species which include iridium acyl and alkyl dihydride intermediates.

The syntheses of Co(eta3-C3H5)(CO)2PR2R' (R, R' = Ph, Me; R, R' = Me, Ph; R = R' = Ph, Cy, CH2Ph) and Co(eta3-C3H5)(CO)(L) (L = dmpe and dppe) are described, and X-ray structures for Co(eta3-C3H5)(CO)(dppe) and the PPh2Me, PCy3 derivatives reported. The relative ability of Co(eta3-C3H5)(CO)2(PR2R') to exchange phosphine for CO follows the trend PMe2Ph < PPh2Me < PCy3 < P(CH2Ph)3 < PPh3. Reactions of the allyl complexes with para-hydrogen (p-H2) lead to the observation of para-hydrogen induced polarisation (PHIP) in both liberated propene and propane. Reaction of these complexes with both CO and H2 leads to the detection of linear acyl containing species Co(COCH2CH2CH3)(CO)3(PR2R') and branched acyl complexes Co(COCH(CH3)2)(CO)3(PR2R') via the PHIP effect. In the case of PPh2Me, additional signals for Co(COCH2CH2CH3)(CO)2(PPh2Me)(propene) and Co(COCH(CH3)2)(CO)2(PPh2Me)(propene) are also detected. When the reactions of H2 and diphenylacetylene are studied with the same precursor, Co(CO)3(PPh2Me)(CHPhCH2Ph) is seen. Studies on how the appearance and ratio, of the PHIP enhanced signals vary as a function of reaction temperature and H2 : CO ratio are reported. These profiles are used to learn about the mechanism of catalysis and reveal how the rates of key steps leading to linear and branched hydroformylation products vary with the phosphine. These data also reveal that the PMe2Ph and PPh2Me based systems yield the highest selectivity for linear hydroformylation products.