110903-79-2Relevant academic research and scientific papers
New adamantane-like mercury-chalcogen cages. Synthetic and multinuclear (31P, 77Se, 199Hg) NMR study of [(μ-ER)6(HgL)4]2+ (E = S or Se; L = tertiary phosphine or arsine) and related species with mixed ligands
Dean, Philip A. W.,Vittal, Jagadese J.,Trattner, Marion H.
, p. 4245 - 4251 (2008/10/08)
Reaction between HgL2(ClO4)2, Hg(ER)2, and L in a 1:3:2 ratio produces the isolable salts [(μ-ER)6(HgL)4](ClO4)2 (L = PPh3, ER = SePh, SPh, SMe, or SEt; L = AsPh3, ER = SPh; L = PEt3, ER = SePh or SPh). Multinuclear (31P, 77Se, 199Hg) NMR was used to demonstrate the adamantanoid structure of the cations in these salts as well as in those with L = PPh3 and ER = S-n-Pr, S-n-Bu, or S-n-C5H11, which were studied in situ. To confirm that the new cations contain the hitherto unobserved (μ-ER)6Hg4 core, several series of clusters with mixed ligands were investigated (as ClO4- salts) by the multinuclear NMR technique also. The systems [(μ-ER)6(HgL)4]2+-[(μ-ER) 6(HgL′)4]2+ (ER = SePh, L = PPh3, L′ = PEt3; ER = SPh, L = PPh3, L′ = PEt3 or AsPh3) give the series [(μ-ER)6(HgL)4-n(HgL′)n]2+ (n = 0-4). The related species [(μ-SPh)6(HgPPh3)4-n(HgSbPh 3)n]2+ (n = 0-2 and possibly 3) were produced from Hg(PPh3)2(ClO4)2, Hg(SPh)2, and SbPh3. From the notably rich 31P and 199Hg NMR spectra of the system [(μ-SPh)6(HgPPh3)4] 2+-[(μ-SePh)6(HgPPh3)4] 2+ it was possible to demonstrate the existence of every possible mixed-chalcogen core in the series [(μ-SPh)6-m(μ-SePh)m(HgPPh3) 4]2+ (m = 0-6). The new (μ-SR)6Hg4 cages are possible models for the proposed Hg4(Cys)11 cluster in Hg7-metallothionein.
