Abstract
Pd dinuclear complexes bridged with pyridylphosphine ligand such as Pd2(Ph2PPy)2X2 (Ph2PPy: diphenyl-2-pyridylphosphine, X: Cl, Br, I, OCN, SCN, NO2, N3) were investigated as catalysts for direct synthesis of diphenyl carbonate (DPC) by oxidative carbonylation of phenol using carbon monoxide (CO) and air. Pd2(Ph2PPy)2X2/redox catalyst/ammonium halide system were found to be more effective than not only conventional PdBr2/Ce(Trop)4 (Trop: tropolonate)/(Ph3P=)2NBr (bis(triphenylphosphoranylidene)ammonium bromide) system but Pd2(dpm)2X2 (dpm: bis(diphenylphosphino)methane)/Mn(TMHD)3 (TMHD: 2,2,6,6-tetramethyl-3,5-hepentanedionate)/(Ph3P=)2NBr system too. The best efficiency was obtained by using Pd2(Ph2PPy)2(NO2)2/Ce(TMHD)4/(Ph3P=)2NBr system where TOF reached 19.21 (mol-DPC/mol-Pd h).
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