5,6- and 6,6-Membered Palladium(II) Pincer Complexes Based on Functionalized Carboxamides with Ancillary Sulfur and Nitrogen Donors

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• 作者：Svetlana G. Churusova ; Diana V. Aleksanyan ; Andrei A. Vasil'ev ; Yulia V. Nelyubina ; Valentin V. Novikov ; Alexander A. Pavlov ; Gleb L. Denisov ; Zinaida S. Klemenkova and Vladimir A. Kozlov
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：November 2016
• 年：2016
• 卷：2016
• 期：33
• 页码：5271-5280
• 全文大小：1269K
• ISSN：1099-0682c

文摘

New multidentate ligands have been synthesized by the condensation of 2-(methylsulfanyl)benzoyl chloride with a range of amines bearing ancillary N or S donors. In reactions with PdCl₂(NCPh)₂, the ligands smoothly underwent direct cyclopalladation to give pincer complexes with 5,6- or 6,6-membered fused metallocycles. The oxidation of the sulfide ligands with H₂O₂ afforded the corresponding sulfoxide derivatives, which readily formed analogous pincer complexes with the Pd^II ions. The realization of κ³-S,N,X coordination (X = N or S) was confirmed by multinuclear NMR and IR spectroscopic data and, in some cases, X-ray crystallography. An unusual dynamic behavior of the 6,6-membered S,N,S complex with an organophosphorus ligand was additionally studied by the ROESY technique. All of the palladocycles obtained were tested as precatalysts for the Suzuki cross-coupling of aryl bromides with arylboronic acids, which allowed us to evaluate the main structure–activity relationships.