SYNTHESIS OF NEW KETONYL PALLADIUM(II) AND PLATINUM(II) COMPLEXES WITH NITROGEN-DONOR LIGANDS - CRYSTAL-STRUCTURE OF [PT(CH2C(O)ME)(2)(BPY)]

Complexes [MCl2L2] (M = Pd, Pt; L-2 = 2,2'-bipyridine (bpy) or Me2N(CH 2)(2)NMe2 (tmeda)) react with ketones MeC(O)R (R = Me, Et) in the pres ence of bases (Ag2O or M'OH (M' = Na, K)) to give the new types of ket onyl palladium(II) and platinum(II) complexes [M(CH2C(O)R)ClL2] (M = P d, L-2 = N,N,N',N'-tetramethylethylenediamine = tmeda; M = Pt, L-2 = 2 ,2'-bipyridine = bpy) and [Pt(CH2C(O)R)(2)L-2] (R = Me, Et, L-2 = bpy) Oxidative addition of chloroacetone on [Pt(dba)(2)] in the presence o f bpy also yields [Pt{CH2C(O)R}ClL2]. [Pd(CH2C(O)Me)Cl(tmeda)] reacts with PhNHNH2 in the presence of TlOTf (OTf = CF3SO3) to give the cyclo metalated complex [Pd(CH2C(Me)=NNH(Ph))(tmeda)]OTf. The crystal struct ure of [Pt(CH2C(O)Me)(2)(bpy)] has been determined. The platinum atom is in a distorted square-planar environment. The strong trans influenc e of the acetonyl ligand promotes the lengthening of both Pt-N bonds ( 2.082(3) and 2.091(3) Angstrom) with concomitant narrowing of the NPtN bond angle (78.89(13)degrees).