Journal
DALTON TRANSACTIONS
Volume 40, Issue 7, Pages 1535-1546Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt01154a
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- Russian Basic Research Foundation [08-03-00508]
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Novel unsymmetrical SCS'-pincer ligands, 1-[PhNHC(S)]-3-[Ph2P(S)NH]-C6H4 (3) and 1-[PhNHC(S)]-3-[Ph2P(S)O]C6H4 (7), bearing a thiocarbamoyl moiety in combination with thiophosphorylamino- and thiophosphoryloxy-donating groups, respectively, were obtained via thiophosphorylation of 3-amino- and 3-hydroxy-benzoic acid (thio)anilides 1 and 6. Direct cyclometallation of the central benzene ring in the ligands 3 and 7 in reaction with (PhCN)(2)MCl2 (M = Pd, Pt) as a metal precursor afforded kappa(3)-SCS'-hybrid pincer complexes 8, 9 with 5- and 6-membered fused metallacycles in good to high yields (67-95%). The complexes 8 and 9 were characterized by multinuclear NMR (P-31, H-1, C-13) and IR spectroscopy as well as single-crystal X-ray crystallography. Palladium complexes 8a and 9a were shown to be active catalysts for the Suzuki-Miyaura cross-coupling reaction. In the solid state the ligands 3 and 7 as well as their Pt(II) and Pd(II) complexes 8 and 9 are luminescent at 300 K. The emission of the complexes has the different origin depending on the metal nature.
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