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)
J. Ruiz et al., 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), Inorganica Chimica Acta, 281(2), 1998, pp. 165-173
The di-mu-hydroxo complexes [NBu4](2)[{(C6X5)(2)M(mu-OH)(2)}(2)] (M=Pd
or Pt; X=F or Cl) react with heterocyclic thiones H(LL') (1:2 molar r
atio) to give the heterocyclic-2-thiolate complexes [NBu4][(C6X5)(2)M(
eta(2)-LL')] (LL' = pyridine-2-thiolate (pyS), pyrimidine 2-thiolate (
pyrimS), 2,6-dimethyl-5-oxo-1,2,4-triazine-3-thiolate (MetazS), 6-meth
yl-5-oxo-1,2,4-triazine-3-thiolate (MetazS)) or [NBu4](2)[{(C6F5)(2)M(
mu-eta(2)-MeimidS)}(2)] (MeimidS = methylimidazole-2-thiolate). The va
riable-temperature H-1 NMR spectra of the complexes [NBu4] [(C6X5)(2)M
(eta(2)-LL')] over the range -50 to +60 degrees C are all static, but
those of the methylimidazole-2-thiolate complexes [NBu4](2)[{(C6F5)(2)
M(mu-eta(2)-MeimidS)}(2)] (M=Pd and Pt) suggest the existence of dynam
ic chemical processes involving both dimeric and monomeric species. Cr
ystallization of [NBu4](2)[{(C6F5)(2)Pd(mu-eta(2)-MeimidS)}(2)] from w
et dichloromethane-hexane-ether afford the mixed complex 4](2)[{(C6F5)
(2)Pd}(2)(mu-OH)(mu-eta(2)-MeimidS)]. The analogous mixed-platinum com
plex u4](2)[{(C6F5)(2)Pt}(2)(mu-OH)(mu-eta(2)-MeimidS)] was prepared b
y reaction of [NBu4](2)[{(C6X5)(2)Pt(mu-OH)(2)}(2)] with the correspon
ding heterocyclic thione H(LL') in 1:1 molar ratio. The crystal struct
ure of [NBu4](2)[{(C6F5)(2)Pd(mu-eta(2)-MeimidS)}(2)], determined by X
-ray diffraction, confirmed the dimeric structure with a head-to-tail
arrangement. C64H82F20N6Pd2S2, orthorhombic Pca2(1), a = 19.552(8), b
= 25.160(3), c = 14.727(3) Angstrom, Z = 4. (C) 1998 Elsevier Science
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