Cyclopalladation of meta-(Diphenylthiophosphoryloxy)benzaldimines: NCS and Unexpected NCO 5,6-Membered Pincer Palladium Complexes

作者: V. A. Kozlov , D. V. Aleksanyan , Yu. V. Nelyubina , K. A. Lyssenko , A. A. Vasil’ev

DOI: 10.1021/OM9009894

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摘要: Unsymmetrical NCS-pincer ligands of a new type, namely, m-(diphenylthiophosphoryloxy)benzaldimines 3 (1-[Ph2P(S)O]-3-[CH═NR]-C6H4, R = OMe (3a), Ph (3b), tBu (3c)), were obtained in two steps starting from commercially available 3-hydroxybenzaldehyde. These easily underwent cyclopalladation at the C-2 position central benzene ring reaction with PdCl2(PhCN)2 or benzene−methanol solutions to afford corresponding hybrid pincer complexes 4a−c five- and six-membered fused metallacycles moderate good yields. The same dichloromethane followed by treatment alcohol resulted unexpected formation related NCO-palladacycles 5a,b, along above NCS-complexes. Complexes 5 present products formal oxidation P═S group ligand, which apparently proceeds metal ion coordination sphere. Realization κ3-NCS κ3-NCO respectively, was unambiguously confirmed X-ray diffraction...

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