Synthesis of New Ketonyl Palladium(II) and Platinum(II) Complexes with Nitrogen-Donor Ligands. Crystal Structure of [Pt{CH2C(O)Me}2(bpy)]

Complexes [MCl 2 L 2 ] (M = Pd, Pt; L 2 = 2,2‘-bipyridine (bpy) or Me 2 N(CH 2 ) 2 NMe 2 (tmeda)) react with ketones MeC(O)R (R = Me, Et) in the presence of bases (Ag 2 O or M‘OH (M‘ = Na, K)) to give the new types of ketonyl palladium(II) and platinum(II) complexes [M{CH 2 C(O)R}ClL 2 ] (M = Pd, L 2 = N, N, N ‘, N ‘-tetramethylethylenediamine = tmeda; M = Pt, L 2 = 2,2‘-bipyridine = bpy) and [Pt{CH 2 C(O)R} 2 L 2 ] (R = Me, Et, L 2 = bpy). Oxidative addition of chloroacetone on [Pt(dba) 2 ] in the presence of bpy also yields [Pt{CH 2 C(O)R}ClL 2 ]. [Pd{CH 2 C(O)Me}Cl(tmeda)] reacts with PhNHNH 2 in the presence of TlOTf (OTf = CF 3 SO 3 ) to give the cyclometalated complex [Pd{CH 2 C(Me) NNH(Ph)}(tmeda)]OTf. The crystal structure of [Pt{CH 2 C(O)Me} 2 (bpy)] has been determined. The platinum atom is in a distorted square-planar environment. The strong trans influence of the acetonyl ligand promotes the lengthening of both Pt−N bonds (2.082(3) and 2.091(3) Å) with concomitant narrowing of the NPtN bond angle (78.89(13)°).