Open AccessStructural Preferences in Phosphanylthiolato Platinum(II) Complexes
Author(s) -
Duran Josep,
Polo Alfonso,
Real Julio,
BenetBuchholz Jordi,
Solà Miquel,
Poater Albert
Publication year - 2016
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201500136
Subject(s) - chemistry , triclinic crystal system , crystallography , monoclinic crystal system , oxidative addition , platinum , palladium , stereochemistry , density functional theory , trans effect , crystal structure , computational chemistry , catalysis , biochemistry
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(SCH 2 CH 2 PPh 2 ‐κ 2 P,S ) 2 ] ( 1 ) was obtained in good yields by direct base‐free substitution reaction of the corresponding phosphanylthiol (HSCH 2 CH 2 PPh 2 ) with K 2 PtCl 4 or by oxidative addition of the same phosphanylthiol to Pt(PPh 3 ) 4 . In agreement with the antisymbiosis rule, complex 1 shows a cis ‐P,P arrangement in solid state crystallizing in the monoclinic system ( C 2 /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 [PtCl 2 (1,5‐cyclooctadiene)] with one equivalent of the same phosphanylthiol produce the trinuclear complex [PtCl(μ‐SCH 2 CH 2 PPh 2 ‐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 Pt 3 S 3 cycle in skew‐boat conformation. This preference for the trinuclear structure was rationalized mechanistically and through conceptual DFT.