Synthesis and reactivity of acetylacetonato-Cγ complexes of MII (M Pd or Pt): X-ray crystal structure of [Pd(C6F5)(OOCPh)(bipy)]·CHCl3

Abstract Acetylacetonato- C γ complexes of stoichiometry [M(C 6 X 5 )(acac- C γ )(NN)] (M  Pd; X  F or Cl; NN = 1,10-phenanthroline or 2,2′-bipyridine) (MPt; XF; NN = 1,10-phenanthroline (phen), or 2,2′-bipyridine (bipy)) have been obtained by treatment of the acetylacetonato- O , O ′ complexes [M(C 6 X 5 )(acac- O , O ′)(tht)] (tht = tetrahydrothiophene) with the corresponding NN base in 1 1 molar ratio. Complexes [Pd(C 6 F 5 )(acac- C γ )(phen)] ( 1 ) and [Pd(C 6 F 5 )(acac- C γ )(bipy)] ( 2 ) react with organic substrates containing acidic hydrogen atoms [HR], yielding the corresponding complexes [Pd(C 6 F 5 )(R)(NN)] (R = CF 3 COO, CH 3 COO, PhCOO, PhS or P(S)Ph 2 ). However, the reaction of 2 with HPPh 2 affords the dinuclear phosphido-bridged complex [{Pd(μ-PPh 2 )(C 6 F 5 )(HPPh 2 )} 2 ]. All complexes have been characterized by spectroscopic methods (IR and 1 H, 19 F and 13 P{ 1 H}NMR) and the molecular structure of [Pd(C 6 F 5 )(OOCPh)(bipy)]·CHCl 3 ( 12 ) has been determined by X-ray diffraction methods.