Structural Preferences in Phosphanylthiolato Platinum(II) Complexes.
The transition-metal complexes of heterotopic phosphanylthiolato ligands are useful in various reactions which depend on the stereochemistry of the complexes. Bis-chelate complex [Pt(SCH2CH2PPh2-κ(2) P,S)2] (1) was obtained in good yields by direct base-free substitution reaction of the corresponding phosphanylthiol (HSCH2CH2PPh2) with K2PtCl4 or by oxidative addition of the same phosphanylthiol to Pt(PPh3)4. In agreement with the antisymbiosis rule, complex 1 shows a cis-P,P arrangement in solid state crystallizing in the monoclinic system (C2/c). Density functional theory (DFT) calculations on 1 reveal the right characteristics for the preferred cis-P,P arrangement, rationalizing its formation. Direct base-free reaction of [PtCl2(1,5-cyclooctadiene)] with one equivalent of the same phosphanylthiol produce the trinuclear complex [PtCl(μ-SCH2CH2PPh2-κ(2) P,S)]3 (2) instead of the binuclear structure common in palladium and nickel derivatives. Crystals of 2 are triclinic (P 1‾ ) showing a sulfur-bridging edge-sharing cyclic trinuclear complex with square-planar coordination geometry around the platinum atoms and a Pt3S3 cycle in skew-boat conformation. This preference for the trinuclear structure was rationalized mechanistically and through conceptual DFT.
Departament de Química Universitat de Girona Campus de Montilivi s/n 17071 Girona Spain.
Josep
0000-0003-2121-6364
J
Duran
Departament de Química Universitat de Girona Campus de Montilivi s/n 17071 Girona Spain.
Alfonso
0000-0002-9665-6025
A
Polo
Departament de Quıímica Universitat Autònoma de Barcelona 08193 Bellaterra Spain.
Julio
0000-0003-1463-7064
J
Real
Institute of Chemical Research of Catalonia ICIQ) Av. Països Catalans 16 43007 Tarragona Spain.
Jordi
0000-0003-3984-3550
J
Benet-Buchholz
Departament de Química Universitat de Girona Campus de Montilivi s/n17071 Girona Spain; Institut de Quıímica Computational i Catàlisi Universitat de Girona Campus de Montilivi s/n 17071 Girona Spain.
Miquel
0000-0002-1917-7450
M
Solà
Departament de Química Universitat de Girona Campus de Montilivi s/n17071 Girona Spain; Institut de Quıímica Computational i Catàlisi Universitat de Girona Campus de Montilivi s/n 17071 Girona Spain.
Albert
0000-0002-8997-2599
A
Poater
P,S ligands; bis-chelate complexes; density functional calculations; platinum; trinuclear complexes