Reaction of the platinum(0) complex [{Pt(LL)} 2 (μ-LL)] [LL = (ViMe 2 Si) 2 O] with PR 3 (R = C 6 H 4 Me-p or C 6 H 1 1 -c) or PPh 2 CH 2 CBu t 2 OH yields, by displacement of the bridging vinylsiloxane ligand, complexes having both a phosphine and a vinylsiloxane as co-ligands. There is evidence for interaction between the platinum atom and the OH moiety in [Pt(LL)(PPh 2 CH 2 CBu t 2 OH)].Reaction of the analogous nickel(0) complex [{Ni(LL)} 2 (μ-LL)] with a tertiary phosphine yields [Ni(LL)PR 3 ] (R = Ph, C 6 H 1 1 -c or C 6 H 4 Me-p). The zinc reduction of [Ni(PPh 3 ) 2 Cl 2 ] in the presence of (ViPh 2 Si) 2 O (PLL) yields the complex [Ni(PLL)PPh 3 ].X-ray molecular structures of the crystalline complexes [Pt(LL)P(C 6 H 4 Me-p) 3 ], [Pt(LL)(PPh 2 CH 2 CBu t 2 OH)], [Ni(LL){P(C 6 H 1 1 -c) 3 }] and [Ni(PLL)(PPh 3 )] show a trigonal planar metal environment and chair conformation for the M(LL) and M(PLL) units.