6533b826fe1ef96bd1284931

RESEARCH PRODUCT

Coordination properties of imino(2-pyridyl)methylpalladium(II) compounds. Preparation and thermal rearrangement of binuclear adducts with palladium(II) and platinum(II) chlorides

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Abstract The imino(2-pyridyl)methylpalladium(II) compound py-2-C(R′)NR (R = C 6 H 4 OMe-p, R′ = trans-PdCl(PPh 3 ) 2 ) reacts with [PdCl 2 (CH 2 CHPh)] 2 , [PdCl 2 - (NCMe) 2 ], and K[PtCl 3 (CH 2 CH 2 )] to give binuclear complexes [MCl 2 {py-2- C(R′)NR}] (M = Pd, Pt), in which the α-diimino group acts as a chelating bidentate ligand. In hot 1,2-dichloroethane, these complexes undergo a PPh 3 and chloride ligand exchange at rates which depend markedly on the metal M (Pd ⪢ Pt), to yield the new derivatives [MCl(PPh 3 ){py-2-C(cis-PdCl 2 (PPh 3 ))NR}]. The ligand exchange is followed by a much slower decomposition to [MCl 2 (PPh 3 ) 2 ]. Labile intermediates of the same type, [MCl(PPh 3 ){RNC(cis-PdCl 2 (PPh 3 ))C(R″)NR}], are formed also in the thermal decomposition of [MCl 2 {RNC(R′)C(R″)NR}] (R = C 6 H 4 OMe-p; R′ = trans-PdCl(PPh 3 ) 2 ; R″ = H, Me). The reactions of the dimethyldithiocarbamate derivative py-2-C(Pd(dmtc)(PPh 3 ))NR (R = C 6 H 4 OMe- p) with K[PtCl 3 (CH 2 CH 2 )] and [PdCl 2 (NCMe) 2 ] yield the different products [PtCl 2 py-2-C(Pd(dmtc)(PPh 3 ))NR] and [Pd(dmtc)py-2-C(cis-PdCl 2 (PPh 3 ))NR], respectively.