The ligands, PhPNXMe (1), PhPNXPh (2), and PhPNSMe (3), (PhPNX = 2-Ph2P-C6H4CH[double bond, length as m-dash]NC6H4X-2; X = O, S) have been prepared. A range of new ruthenium complexes were synthesised using these and related ligands, namely: [{RuCl(PhPNO)}2Cl] (4), [Ru(PhPNO)2] (5), [RuCl(PhPNXR)(PPh3)]BPh4 [X = O, R = Me (6); X = O, R = Ph (7); X = S, R = Me (8)], [{RuCl(PhPNX'R)}2Cl]X [X' = O, R = Me, X = Cl(-) (9); X' = S, R = Me, X = BPh4(-) or PF6(-) (10)], and [RuCl(PhPNO-eta 6C6H5)]BPh4 (11). The catalytic activity of these complexes with respect to the hydrosilyation of acetophenone and the hydrogenation of styrene has been investigated, giving an insight into the requirements for an active complex in these reactions.