5,6-Membered palladium pincer complexes of 1-thiophosphoryloxy-3-thiophosphorylbenzenes. Synthesis, X-ray structure, and catalytic activity

• Published in: Dalton transactions : an international journal of inorganic chemistry no. 40; pp. 8657 - 8666
• Main Authors: Kozlov, V A, Aleksanyan, D V, Nelyubina, Yu V, Lyssenko, K A, Gutsul, E I, Vasil'ev, A A, Petrovskii, P V, Odinets, I L
• Format: Journal Article
• Language: English
• Published: England 28.10.2009
• Subjects: Benzene Derivatives - chemistry; Catalysis; Crystallography, X-Ray; Models, Molecular; Molecular Structure; Organometallic Compounds - chemical synthesis; Organometallic Compounds - chemistry; Organophosphorus Compounds - chemistry; Palladium - chemistry
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/b907644a

Novel unsymmetrical ligands, 1-thiophosphoryloxy-3-thiophosphorylbenzenes 3a-d, bearing phosphine sulfide and thiophosphoryloxy moieties as coordinating sites, were found to undergo cyclometalation at the C-2 position of the central benzene ring in a reaction with bis(benzonitrile)palladium dichloride affording rare examples of nonsymmetrical pincer complexes, namely [2-{(thiophosphoryl)oxy}-6-(diphenylthiophosphoryl)phenyl]palladium chlorides 4a-d, containing 5- and 6-membered fused metallacycles with kappa3-SCS'-coordination. Molecular structures of the complexes were characterized by X-ray diffraction. These complexes demonstrated high catalytic activity for the Suzuki cross-coupling reactions of aryl bromides with phenylboronic acid.