Toggle Main Menu Toggle Search

Open Access padlockePrints

Preparation, structure, and properties of the corner-shared double cubes [Mo6HgQ8(H2O)18]8+ (Q = S, Se) and tungsten analogues

Lookup NU author(s): Dr Maxim Sokolov, Mi-Sook Seo, Professor William Clegg, Emeritus Prof Alfred Sykes

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


Abstract

The purple corner-shared double cube [Mo6HgS8(H2O)18]8+ derivative of green [Mo3S4(H2O)9]4+, obtained under air-free conditions by the reaction with HgO (metal), is also formed with HgI2. The HgI2 reaction is accounted for by the disproportionation HgI2 ?? HgO + HgII, which is a source of HgO. X-ray crystallographic information on the blue partially Cl- substituted cucurbituril supramolecular assemblies [Mo6HgQ8Cl4 (H2O)14] (C36H36 N24O12)Cl4·14H2O (1) and of the Se analogue [Mo6HgSe8Cl4 (H2O)14] (C36H36 N24O12)Cl4·14H2O (2) have been determined. The product [W6HgSe8Cl4(H2O)14] (C36H36N24 O12) Cl4·14H2O (3) has also been obtained, but there is no evidence for [W6HgS8(H2O)18]8+ and related forms. The formation of [Mo6HgS8(H2O)18]8+ by the reaction of [Mo3S4 (H2O)9]4+ with HgO under anaerobic conditions maximizes after @O40 h in 2.0 M HCl, but requires longer reaction time (@O120 h) in 2.0 M Hpts (p-toluenesulfonic acid) and in 2 M HClO4 (@O6 days). In 2.0 M HCl there is little absorbance increase until [Mo3S4(H2O)9]4+ exceeds 1.2 x 10-3 M, which is explained by a dependence of the formation K (265 M-1) on [Mo3S4 (H2O)94+]2. Furthermore, on dilution of column-purified [Mo6HgS8(H2O)18]8+, Beer's law is not obeyed and equilibria involving 2[Mo3S4(H2O)9]4+ are apparent. The kinetics of formation of [Mo6HgS8(H2O)18]8+ is first-order in [Mo3S4(H2O)9]4+, consistent with rate-determining formation of the single cube [Mo3HgS4(H2O)x]4+. The oxidations of [Mo6HgS8(H2O)18]8+ with [Fe(H2O)6]3+ and [Co(dipic)2]- are complicated by the release of [Hg(H2O)6]2+, which also functions as an oxidant. Similar results are obtained for [Mo6HgSe8(H2O)18]8+ and the less extensively studied [W6HgSe8(H2O)18]8+.


Publication metadata

Author(s): Fedin VP, Sokolov M, Lamprecht GJ, Hernandez-Molina R, Seo M-S, Virovets AV, Clegg W, Sykes AG

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2001

Volume: 40

Issue: 26

Pages: 6598-6603

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic010362n

DOI: 10.1021/ic010362n

PubMed id: 11735468


Altmetrics

Altmetrics provided by Altmetric


Share