The synthesis of the benzyl phosphinothioether derivatives Ph2PCH2CH(Et)SR and their corresponding palladium complexes are reported, where R = CH2Ph (3), R = CH2-3,5-Me-C6H3 (4) and R = 1-CH2C10H7 (5). Crystallographic data obtained for the complexes Pd(3)Cl2 and Pd(4)Cl2 show intra- and inter-molecular π–π interactions between the aromatic rings on the P and S substituents, and NOE experiments for Pd(4)Cl2 show that these interactions persist in solution. The performance of the phosphinothioether palladium complexes in aryl–aryl cross-coupling reactions is compared with that of the corresponding complex of the parent phosphinothiolato ligand Ph2PCH2CH(Et)S− (1). High turnover numbers up to 2000000 are reported for the coupling of bromobenzene, using the palladium dimer [Pd(1)I]2 as the catalyst precursor. Kinetic studies show a linear dependence of the reaction on catalyst loading. The effect of other variables on the cross-coupling reaction, such as temperature, solvent and base, is also reported.
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