Reactivity of Labile Triosmium Complexes, [Os3(CO)10(MeCN)2] and [Os3(CO)10(µ-H)2] with Tetraethylthiuram Disulfide (Disulfiram)

IF 2.7 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Nikhil C. Bhoumik, Md. Nazmul Huda, Vladimir N. Nesterov, Graeme Hogarth, Shariff E. Kabir, Jagodish C. Sarker
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引用次数: 0

Abstract

Reactions of the anti-alcohol drug disulfiram (tetraethylthiuram disulphide = Et4TDS) with low valent triosmium complexes are described. Room temperature reaction with [Os3(CO)10(MeCN)2], affords three new open polynuclear clusters, [Os3(CO)10(S2CNEt2)2] (1), [Os4(CO)1231(C),κ2(O,O)-CO2}(S2CNEt2)(µ-S2CNEt2)] (2) and [Os3(CO)93-SCNEt2){µ-SC(O)NEt2}] (3) together with the known mononuclear complex cis-[Os(CO)2(S2CNEt2)2] (4). All result from oxidative-addition of disulfiram to the triosmium centre, with 2 also capturing CO2, while cluster 3 has undergone further C–S bond scission and partial oxidation of one of the generated thiocarboxamide ligands. With [Os3(CO)10(µ-H)2], complexes 1 and 4 are also formed along with previously reported [Os3(CO)10(µ-S2CNEt2)(µ-H)] (5), [Os3(CO)93-S2CNEt2)(µ-H)] (6), and the new cluster, [Os3(CO)9(µ-S2CNEt2)(µ-H)] (8), which is an isomer of 6. The product distribution is rationalized by completing pathways following the oxidative-addition of disulfiram. Thus, reductive-elimination of H2 affords 1, which in turn converts to 4, while reductive-elimination of the (unstable) dithiocarbamic acid, Et2NCS2H, leads to the formation of 5, which can further lose CO to afford isomers 6 and 8. Heating disulfiram with [Os3(CO)12] at 110 °C predominantly affords 4, together with smaller amounts of the novel trithiocarbamate complex, cis-[Os(CO)2(S2CNEt2)(S3CNEt2)] (9). All the compounds have been characterized by elemental analysis, IR and 1H NMR spectroscopy, together with single crystal X-ray diffraction analysis of six molecules.

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来源期刊
Journal of Cluster Science
Journal of Cluster Science 化学-无机化学与核化学
CiteScore
6.70
自引率
0.00%
发文量
166
审稿时长
3 months
期刊介绍: The journal publishes the following types of papers: (a) original and important research; (b) authoritative comprehensive reviews or short overviews of topics of current interest; (c) brief but urgent communications on new significant research; and (d) commentaries intended to foster the exchange of innovative or provocative ideas, and to encourage dialogue, amongst researchers working in different cluster disciplines.
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