Activation of C–S Bond by Group 10 Metal Complexes: Reaction of Phosphine Ligand Tethered with Three tert-Butylthiophenyl Groups with Group 10 Metal Compounds

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Abstract A new PS3-type tripodal tetradentate ligand, P(2-t-BuSC6H4)3 (1b), was synthesized by reaction of PCl3 with 2-t-BuS(C6H4)Li. Reaction of ligand 1b with NiCl2·6H2O resulted in the elimination of t-BuCl to afford the corresponding 5-coordinate nickel complex, [NiCl{P(2-SC6H4)(2-t-BuSC6H4)2}] 6. In addition, ligand 1b reacted with [PdCl2(PhCN)2] and [PtCl2(cod)] to give 4-coordinate square planar palladium and platinum complexes, [MCl{P(2-SC6H4)(2-t-BuSC6H4)2}] (7: M = Pd, 8: M = Pt), respectively, via the elimination of t-BuCl. Further elimination of t-BuCl from palladium complex 7 proceeded by heating of 7 in CDCl3 at 100 °C for 4 h to form dipalladium complex, [Pd2{P(2-SC6H4)2(2-t-BuSC6H4)}2] (9). The isopropyl-substituted palladium and platinum complexes, [PdCl{P(2-i-PrSC6H4)3}]Cl (3a) and [PtCl2{P(2-i-PrSC6H4)3}] (5), also underwent the elimination of i-PrCl by the thermolysis in CDCl3 at 60 °C to afford the corresponding complexes, [MCl{P(2-SC6H4)(2-i-PrSC6H4)2}] (11: M = Pd, 12: M = Pt). The structures of these complexes were determined by NMR spectroscopy, elemental analyses, and X-ray crystallography.