Anna V. Konkova, Darya V. Evtushok, Natalia V. Kuratieva, Anton A. Ivanov, Michael A. Shestopalov
{"title":"基于[Mo2O2S2]的硫代钼酸盐及其与吡唑和三唑的反应活性","authors":"Anna V. Konkova, Darya V. Evtushok, Natalia V. Kuratieva, Anton A. Ivanov, Michael A. Shestopalov","doi":"10.1007/s10876-024-02595-z","DOIUrl":null,"url":null,"abstract":"<p>Extending the family of oxothiomolybdates, the interaction of the cyclic anion [Mo<sub>8</sub>O<sub>8</sub>S<sub>8</sub>(OH)<sub>8</sub>(C<sub>2</sub>O<sub>4</sub>)]<sup>2−</sup> and the complex [Mo<sub>4</sub>O<sub>4</sub>S<sub>4</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>5</sub>]<sup>6−</sup> with organic compounds of the azole series—pyrazole (pzH) and 1,2,4-triazole (trzH) in water solution and in the melt of ligands was investigated. In water solution pyrazole plays only the role of cation (upon protonation) to form the complex (pzH<sub>2</sub>)<sub>2</sub>[Mo<sub>2</sub>O<sub>2</sub>S<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]. While in the reaction in melt of pzH in the case of the initial cyclic anion, the resulting anionic product [Mo<sub>6</sub>O<sub>6</sub>S<sub>6</sub>(pz)<sub>6</sub>(MoO<sub>4</sub>)]<sup>2−</sup> represents a pioneering example of a cyclic oxothiometalate {Mo<sub>6</sub>} anchored by the coordination of six bridging pyrazolates (pz), complemented by a MoO<sub>4</sub><sup>2−</sup> core. At the same time, the interaction of [Mo<sub>4</sub>O<sub>4</sub>S<sub>4</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>5</sub>]<sup>6−</sup> with pzH and trzH melts yields the binuclear clusters [Mo<sub>2</sub>O<sub>2</sub>S<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>L<sub>2</sub>]<sup>2−</sup>, where L = pzH or trzH. The composition and structures of the compounds were determined using a variety of physicochemical methods, including single-crystal X-ray diffraction analysis.</p>","PeriodicalId":618,"journal":{"name":"Journal of Cluster Science","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"[Mo2O2S2]-Based Oxothiomolybdates and Their Reactivity with Pyrazole and Triazole\",\"authors\":\"Anna V. Konkova, Darya V. Evtushok, Natalia V. Kuratieva, Anton A. Ivanov, Michael A. Shestopalov\",\"doi\":\"10.1007/s10876-024-02595-z\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Extending the family of oxothiomolybdates, the interaction of the cyclic anion [Mo<sub>8</sub>O<sub>8</sub>S<sub>8</sub>(OH)<sub>8</sub>(C<sub>2</sub>O<sub>4</sub>)]<sup>2−</sup> and the complex [Mo<sub>4</sub>O<sub>4</sub>S<sub>4</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>5</sub>]<sup>6−</sup> with organic compounds of the azole series—pyrazole (pzH) and 1,2,4-triazole (trzH) in water solution and in the melt of ligands was investigated. In water solution pyrazole plays only the role of cation (upon protonation) to form the complex (pzH<sub>2</sub>)<sub>2</sub>[Mo<sub>2</sub>O<sub>2</sub>S<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]. While in the reaction in melt of pzH in the case of the initial cyclic anion, the resulting anionic product [Mo<sub>6</sub>O<sub>6</sub>S<sub>6</sub>(pz)<sub>6</sub>(MoO<sub>4</sub>)]<sup>2−</sup> represents a pioneering example of a cyclic oxothiometalate {Mo<sub>6</sub>} anchored by the coordination of six bridging pyrazolates (pz), complemented by a MoO<sub>4</sub><sup>2−</sup> core. At the same time, the interaction of [Mo<sub>4</sub>O<sub>4</sub>S<sub>4</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>5</sub>]<sup>6−</sup> with pzH and trzH melts yields the binuclear clusters [Mo<sub>2</sub>O<sub>2</sub>S<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>L<sub>2</sub>]<sup>2−</sup>, where L = pzH or trzH. The composition and structures of the compounds were determined using a variety of physicochemical methods, including single-crystal X-ray diffraction analysis.</p>\",\"PeriodicalId\":618,\"journal\":{\"name\":\"Journal of Cluster Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-04-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Cluster Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1007/s10876-024-02595-z\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Cluster Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s10876-024-02595-z","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
[Mo2O2S2]-Based Oxothiomolybdates and Their Reactivity with Pyrazole and Triazole
Extending the family of oxothiomolybdates, the interaction of the cyclic anion [Mo8O8S8(OH)8(C2O4)]2− and the complex [Mo4O4S4(C2O4)5]6− with organic compounds of the azole series—pyrazole (pzH) and 1,2,4-triazole (trzH) in water solution and in the melt of ligands was investigated. In water solution pyrazole plays only the role of cation (upon protonation) to form the complex (pzH2)2[Mo2O2S2(C2O4)2(H2O)2]. While in the reaction in melt of pzH in the case of the initial cyclic anion, the resulting anionic product [Mo6O6S6(pz)6(MoO4)]2− represents a pioneering example of a cyclic oxothiometalate {Mo6} anchored by the coordination of six bridging pyrazolates (pz), complemented by a MoO42− core. At the same time, the interaction of [Mo4O4S4(C2O4)5]6− with pzH and trzH melts yields the binuclear clusters [Mo2O2S2(C2O4)2L2]2−, where L = pzH or trzH. The composition and structures of the compounds were determined using a variety of physicochemical methods, including single-crystal X-ray diffraction analysis.
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