Abstract
Abstract Complexation of a hybrid P—S ligand o-(ethylphenylphosphino)(ethylthio)benzene (2) with NiCl2. DME (DME = MeOCH2CH2OMe), (CH3CN)2PdCl2, and (CH3CN)2PtCl2 provided [o-C6H4(PEtPh)(SEt)-P,S)MCl2 {3a, M = Ni; 3b, M = Pd, 3c, M = Pt) respectively. Due to the stereogenic center at phosphorus atoms, complexes 3a-c exist as a pair of geometrical isomers, which would interconvert to each other by inversion at the sulfur center. Substitution of chloride by triphenylphosphine occurs in complexes 3b-c to provide [{o-C6H4(PEtPh)(SEt)-P,S}M(PPh3)Cl]Cl {4b, M = Pd; 4c, M = Pt}, but not in 3a. Both triphenylphosphine substituted complexes 4b and 4c readily undergo S-dealkylation to give {o-C6H4(PPhEt)(S)-P, S}MCl(PPh3) {5b, M = Pd; 5c, M = Pt} respectively. The inversion barriers (kJ/mol) of coordinated sulfur centers were determined by NMR spectroscopy: 52 ± 2 for 3a, 60 ± 2 for 3b, 70 ± 2 for 3c, 53 ± 2 for 4b and 58 ± 3 for 4c. During dealkylation of [{o-C6H4(PEtPh)(SEt)-P, S}Pt(PPh3)Cl]Cl (4c) with chloride ...
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