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The regioselectivity of the reaction can be altered by choice of the activating agent: NaH for 1,2- or TMS-O-Tf for 1,4-selectivity.

A family of eight neutral, pseudotetrahedral piano-stool ruthenium complexes C, of the type [RuCl2(p-cymene)(PArPhR)] (Ar = 1-naphthyl, 9-phenanthryl and 2-biphenylyl; R = Me, i-Pr, OMe, –CH2SiMe3 and –CH2SiPh3) have been prepared and characterised, including the X-ray crystal structure for C6 (Ar = 2-biphenylyl; R = i-Pr). These complexes catalyse the asymmetric hydrogen transfer reaction of acetophenone in refluxing 2-propanol in the presence of potassium tert-butoxyde, reaching full conversions and up to 45% ee after 24 h towards the S enantiomer of 1-phenylethanol. Cationic complexes formed upon treatment of C with one equivalent of AgSbF6 or (Et3O)PF6 are active in the cyclopropanation reaction of styrene and α-methylstyrene by ethyl diazoacetate. Low to moderate conversions (up to 58%), diastereoselectivities (up to 40% de), and moderate enantioselectivities (up to 69% ee) have been found. For both reactions, bulky complexes and C6 in particular lead to the best results.

Two groups of P-stereogenic monodentate phosphines containing pendant groups bearing functionalities capable of having secondary interactions, PArPhR (Ar = 2-[(2′,6′-dimethoxy)-1,1′-biphenylyl] and R = OMe (6) or Me (8)) and PMeR(CH2R′) (13, R = t-Bu or 14 R = Fc and R′ = SiMe3 (a), SiMe2Ph (b) or CH2(2-naphthyl) (c)) have been prepared in enantiomerically pure form by the Juge and Evans methodologies and characterised, including the crystal structure for the borane adduct of 12b. Reaction of the phosphines with the Pd dimer [Pd(η3-2-Me-allyl)(μ-Cl)]2 produced neutral allylic complexes C [PdCl(η3-2-Me-C3H4)P∗], which have been characterised in solution and shown to be a mixture of isomers with different absolute configuration at the Pd atom. After abstraction of the chloride ligand by AgBF4, the solutions of cationic complexes have been used as catalyst precursors in the hydrovinylation of styrene under mild conditions. Very good activities (up to 1015 h−1), moderate to good selectivities to 3-phenyl-1-butene and low to moderate enantioselectivities (