US EPA

7740661 

Journal Article 

Reactivity of [NBu4](2)[{(C6X5)(2)M(mu-OH)}(2)] (X = F or Cl; M = Pd or Pt) towards heterocyclic thiones: crystal structure of [NBu4](2)[{(C6F5)(2)Pd(mu-eta(2)-LL ')}(2)] (LL ' = methylimidazole-2-thiolate) 

Ruiz, J; Florenciano, F; Lopez, G; Chaloner, PA; Hitchcock, PB 

1998 

1 

Inorganica Chimica Acta
ISSN: 0020-1693
EISSN: 1873-3255 

Elsevier S.A. 

281 

2 

165-173 

English 

10.1016/S0020-1693(98)00164-9 

WOS:000076626600008 

The di-μ-hydroxo complexes [NBu4]2[{(C6X5) 2M(μ-OH)2}2] (M = Pd or Pt; X = F or Cl) react with heterocyclic thiones H(LL′) (1:2 molar ratio) to give the heterocyclic-2-thiolate complexes [NBu4] [(C6X5)2M(η2-LL′)] (LL′ = pyridine-2-thiolate (pyS), pyrimidine-2-thiolate (pyrimS), 2,6-dimethyl-5-oxo-1,2,4-triazine-3-thiolate (Me2tazS), 6-methyl-5-oxo-1,2,4-triazine-3-thiolate (MetazS)) or [NBu4]2[{(C6F5) 2M(μ-η2-MeimidS)}2] (MeimidS=methylimidazole-2-thiolate). The variable-temperature 1H NMR spectra of the complexes [NBu4] [(C6X5)2M(η2-LL′)] over the range - 50 to +60°C are all static, but those of the methylimidazole-2-thiolate complexes [NBu4]2[{(C6F5) 2M(μ-η2-MeimidS)}2] (M=Pd and Pt) suggest the existence of dynamic chemical processes involving both dimeric and monomeric species. Crystallization of [NBu4]2[{(C6F5)2Pd} 2( (μ-η2-MeimidS)}2] from wet dichloromethane-hexane-ether afforded the mixed complex [NBu4]2[{(C6F5)2Pd} 2(μ-OH)(μ-η2-MeimidS)]. The analogous mixed platinum complex [NBu4]2[{(C6F5)2Pd} 2(μ-OH)(μ-η2-MeimidS)] was prepared by reaction of [NBu4]2[{(C6X5) 2Pt(μ-OH)2}2] with the corresponding heterocyclic thione H(LL′) in 1:1 molar ratio. The crystal structure of [NBu4]2[{(C6F5) 2Pd(μ-η2-MeimidS)}2], determined by X-ray diffraction, confirmed the dimeric structure with a head-to-tail arrangement. C64H82F20N6Pd2S 2, orthorhombic Pca21, a=19.552(8), b=25.160(3), c=14.727(3) Å, Z=4. © 1998 Elsevier Science S.A. All rights reserved. 

palladium complexes; platinum complexes; thione complexes; crystal structures