The orthometalated complex [{Pd(μ-Cl){κ2-P,C-P(OC6H2-2,4-t Bu2)(OC6H3-2,4-tBu2 )2}}2] reacts with phenylboronic acid hydrate and K2CO3 in dimethylacetamide to give [Pd{κ2-P,C-μ2-O-P(O)(C6H2-2 ,4-tBu2)(C6H3-2,4-tBu 2)(DMAc)}]. When the reaction is repeated in dimethylformamide 3,3′,5,5′-tetra-tert-butyl-2,2′-biphenol is isolated. Both compounds have been characterized crystallographically. The reaction of palladium dichloride with PiPr2-(OC6H4-4-Et) in 2-methoxyethanol followed by recrystallization in the presence of ethanol leads to the formation of trans-[PdCl2{PiPr2(OEt)}2], which was also characterized by crystallography. To determine whether related solvolytic processes have a bearing on catalytic activity, the performance of a range of catalysts with "hydrolyzed" and "nonhydrolyzed"ligands was assessed in the Suzuki coupling of aryl bromides. In some cases it was evident that hydrolysis plays a significant role on the catalytic activity; however, this depends not only on the ligand, but also on the combination of ligand and palladium precursor.
