The complexes Pd2Cl2(P-P)2, where (P-P) = µ-bis(diphenylphosphino) methane, dpm, or µ-1,1-bis(diphenylphosphino) ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(µ-Se) (P-P)2, which can be oxidized by t-BuOOH to the µ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2−n,-(SeH)n,(µ-Se) (dpm)2 species (n = 0−2). anti-Pd2Cl2(µ-Se) (dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) Å, b = 24.141(2) Å, c = 18.921(2 Å), β = 106.64(1) °, V = 5243.2(11) ' Å3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I). 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(µ-Se) (P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry