Synthesis and Characterization of Chalcogenolato-Bridged Allyl Palladium Complexes: Versatile Precursors for Palladium Chalcogenides

The complexes [Pd(μ-ER)(η 3 -allyl)] 2 (ER = EMes; E = S, Se; allyl = C 3 H 5, C 4 H 7 ) have been isolated by the reaction of [Pb(ER) 2 ] n with [Pd 2 (μ-Cl) 2 (η 3 -allyl) 2 ]. Similar reactions with [Pb(SeCH 2 CH 2 NMe 2 ) 2 ] n resulted in the formation of a trinuclear complex [Pd 3 Cl 2 (κ 2 -Se,N-SeCH 2 CH 2 NMe 2 )(η 3 -allyl) 3 ]. Treatment of [Pd(μ-SR)(η 3 -C 4 H 7 )] 2 with [Pd(SMes) 2 ] n in 1:1 ratio yielded [Pd 3 (μ-SMes) 4 (η 3 -C 4 H 7 ) 2 ]. These complexes were characterized by elemental analyses and mass, UV−vis, and NMR spectroscopy. The structures of [Pd 2 (μ-EMes) 2 (η 3 -C 4 H 7 ) 2 ] (E = S, Se) were established by single-crystal X-ray diffraction analysis, which revealed a syn configuration. Two new structural motifs for [Pd 3 Cl 2 (κ 2 -Se,N-SeCH 2 CH 2 NMe 2 )(η 3 -C 3 H 5 ) 3 ] and [Pd 3 (μ-SMes) 4 (η 3 -C 4 H 7 ) 2 ] have also been identified. Pyrolysis of [Pd(μ-ER)(η 3 -C 4 H 7 )] 2 yielded palladium chalcogenides, which were characterized by powder XRD and EDAX.