Decarboxylation of (triphenylphosphine)gold(I) carboxylates

Article abstract of DOI:10.1021/om00053a021

(Triphenylphosphine)gold(I) carboxylates Ph₃PAuOC(O)CH(CH₃)₂ (1) and Ph₃PAuOC(O)CH(OH)CH₃ (2) have been synthesized and structurally characterized by single-crystal X-ray diffraction studies. Decarboxylation of these complexes is observed at temperatures under 100°C with the formation of carbon dioxide, metallic gold (mirror), triphenylphosphine, and organic products. The nature of the organic products that are formed depends on the type of carboxylate and the reaction conditions. Decarboxylation of a carboxylate copolymer of polyethylene and acrylic acid (EAA), Dow Chemical PRIMACOR 5980, with [Ph₃PAu]⁺ bound to the carboxylate, is observed to give CO₂, triphenylphosphine, metallic gold, and unsaturated polymer. Structural results: complex 1 triclinic, P1, a = 6.845(1) A?, b = 11.9681(3) A?, c = 13.413 (3) A?, α = 77.45 (2)°, β = 84.80 (2)°, γ = 77.66 (2)°, V = 1046.6 (4) A?³, Z = 2, R = 0.0306, and R_w = 0.0315; complex 2 triclinic, P1, a = 8.681 (3) A?, b = 11.342 (4) A?, c = 12.619 (5) A?, α = 111.74 (3)°, β = 104.37 (3)°, γ = 95.34 (3)°, V = 1094.1 (7) A?³, Z = 2, R = 0.060, and R_w = 0.060.