Synthesis of mono-, di- and tripalladated 1,3,5-benzenetristyryl complexes. CO insertion to give a dipalladated indenone

Abstract

The tribrominated arenes 1,3,5-C₆(E-CHCHAr)₃Br₃ (Ar = Ph, (I), p-To (I′)), add oxidatively to [Pd(dba)₂] ([Pd₂(dba)₃]·dba) in the presence of two equivalents of a phosphine (PPh₃ or PMe₂Ph) to form the monopalladated complexes trans-[Pd{C₆(E-CHCHAr)₃Br₂}Br(L)₂] (Ar = Ph, L = PPh₃ (1a), Ar = p-To, L = PPh₃ (1a′), Ar = Ph, L = PMe₂Ph (1b)), while the reaction in a 1 : 2 : 4 arene : Pd : PMe₂Ph molar ratio affords the dipalladated complex [{trans-PdBr(PMe₂Ph)₂}₂{μ₂-C₆(E-CHCHPh)₃Br}] (2b). Both I and I′ add oxidatively to 3 equivalents of [Pd(dba)₂] in the presence of the chelating N-donor ligand tmeda (N,N,N′,N′-tetramethylethylenediamine) to form the tripalladated complexes [{PdBr(tmeda)}₃{μ₃-C₆(E-CHCHAr)₃}] (Ar = Ph, (3c), p-To (3c′)). Complex 3c reacts with PMe₃ to form [{trans-PdBr(PMe₃)₂}₃{μ₃-C₆(E-CHCHPh)₃}] (3d). Compound 3c also reacts with CO to give the novel dipalladated indenone [2-Ph-4,6-{PdBr(tmeda)}₂-5,7-(E-CHCHPh)₂-inden-1-one] (4). The crystal structures of 1a′ and 1b were determined by X-ray diffraction studies.