The phosphonium diner [-Cy2PCH(OH)CH2-](2)(X)(2), X = Cl-, Br- was used to synthesize and characterize a variety of late transition metal complexes containing chelating phosphino-enolate (PCy2CH=CHO-), imine (PCy2CH2CH=NR, R = Ph, (S)-CHMePh), and oxime (PCy2CH2CH=NOH) ligands. The phosphonium dimer, when deprotected with base, generates the phosphine aldehyde PCy2CH2CHO in situ, which, in the presence of [M(COD)Cl](2), M = Rh, Ir, and a PF6- salt, or [Ni(H2O)(6)][BF4](2), facilitates a condensation reaction with an amine or hydroxylamine to form phosphino-imine or phosphino-oxiine metal complexes [M(COD)(P-N)][PF6] or [Ni(P-N)(2)][X](2) X = ClO4-, BF4-, respectively. In the absence of an amine, phosphino-enolate containing complexes are formed. A neutral Ni(II) complex Ni(PCy2CH=CHO)(2) with trans-bis(phosphino-enolate) ligands which resemble ligands used on nickel for olefin oligomerization, as well as neutral Rh(I) and Ir(I) 1,5-cyclooctadiene complexes M(COD)(PCy2CH=CHO) are characterized. Both the rhodium and iridium complexes are active olefin hydrogenation catalysts. Reaction of the phosphino-aldehyde with Pt(COD)Cl-2 results in the formation of trans-PtCl2(PCy2CH2CHO)(2) with pendant aldehyde groups, and under certain conditions, they undergo an intraligand aldol condensation to form a disphosphine ligand.