{"title":"由早期过渡金属包覆的深度还原多氧钼酸盐与硝基苯的催化加氢","authors":"Xian Xu, Song Lin, Fang Yu and Li Xu*, ","doi":"10.1021/acs.inorgchem.5c00599","DOIUrl":null,"url":null,"abstract":"<p >Deeply reduced polyoxometalates (POMs) capped by early transition metals, [V<sub>3</sub><sup>IV</sup>Mo<sub>6</sub><sup>IV</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>31</sub>py<sub>6</sub>]<sup>2–</sup> (<b>1</b>, py = pyridine) and [V<sub>2</sub><sup>IV</sup>Mo<sub>12</sub><sup>IV</sup>Mo<sub>8</sub><sup>VI</sup>Zn<sub>0.35</sub>H<sub>1.3</sub><sup>+</sup>O<sub>54</sub>py<sub>12</sub>(HNMe<sub>2</sub>)<sub>2</sub>]<sup>2–</sup> (<b>2</b>), were prepared from solvothermal oxidative aggregations of [Mo<sub>3</sub><sup>IV</sup>O<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>6</sub>(H<sub>2</sub>O)<sub>3</sub>]ZnCl<sub>4</sub> and VO(acac)<sub>2</sub> (acac = acetylacetonato). V<sub>3</sub>-capped Mo<sub>6</sub><sup>IV</sup>-<b>1</b> and V-capped Mo<sub>6</sub><sup>IV</sup>-<b>2</b> exhibit 12e-reduced POM structures characteristic of two [Mo<sub>3</sub><sup>IV</sup>O<sub>4</sub>] incomplete cuboidal cluster units bridged by two(one) VO<sub>5</sub> groups in <b>1</b>(<b>2</b>), differing from those linked by SbO<sub>3</sub>/GeO<sub>4</sub>/SbO<sub>3</sub>-pyZnO<sub>4</sub> groups in the previously reported [Sb<sub>2</sub>Mo<sub>6</sub><sup>IV</sup>Mo<sub>2</sub><sup>V</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>32</sub>(OH)<sub>2</sub>py<sub>6</sub>]<sup>2–</sup> (<b>3</b>), [Ge<sub>2</sub>Mo<sub>6</sub><sup>IV</sup>Mo<sub>2</sub><sup>V</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>34</sub>(OH)<sub>2</sub>py<sub>6</sub>]<sup>4–</sup> (<b>4</b>), and [Sb<sub>2</sub>ZnMo<sub>6</sub><sup>IV</sup>Mo<sub>2</sub><sup>V</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>32</sub>(OH)<sub>2</sub>py<sub>7</sub>] (<b>5</b>), respectively. Multiple Mo<sup>IV</sup>···O//Sb<sup>III</sup> Lewis pairs in <b>1</b>–<b>3</b> construct well-organized Lewis catalysis fields (LCFs) featuring extensive Lewis acid–base synergistic interactions, which account for their excellent catalytic performance in heterogeneous hydrogen-transfer hydrogenation (HTH) reduction of nitrobenzene to aniline under mild conditions.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 25","pages":"12560–12569"},"PeriodicalIF":4.7000,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Deeply Reduced Polyoxomolybdates Capped by Early Transition Metals with Catalytic Hydrogenation of Nitrobenzene\",\"authors\":\"Xian Xu, Song Lin, Fang Yu and Li Xu*, \",\"doi\":\"10.1021/acs.inorgchem.5c00599\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Deeply reduced polyoxometalates (POMs) capped by early transition metals, [V<sub>3</sub><sup>IV</sup>Mo<sub>6</sub><sup>IV</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>31</sub>py<sub>6</sub>]<sup>2–</sup> (<b>1</b>, py = pyridine) and [V<sub>2</sub><sup>IV</sup>Mo<sub>12</sub><sup>IV</sup>Mo<sub>8</sub><sup>VI</sup>Zn<sub>0.35</sub>H<sub>1.3</sub><sup>+</sup>O<sub>54</sub>py<sub>12</sub>(HNMe<sub>2</sub>)<sub>2</sub>]<sup>2–</sup> (<b>2</b>), were prepared from solvothermal oxidative aggregations of [Mo<sub>3</sub><sup>IV</sup>O<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>6</sub>(H<sub>2</sub>O)<sub>3</sub>]ZnCl<sub>4</sub> and VO(acac)<sub>2</sub> (acac = acetylacetonato). V<sub>3</sub>-capped Mo<sub>6</sub><sup>IV</sup>-<b>1</b> and V-capped Mo<sub>6</sub><sup>IV</sup>-<b>2</b> exhibit 12e-reduced POM structures characteristic of two [Mo<sub>3</sub><sup>IV</sup>O<sub>4</sub>] incomplete cuboidal cluster units bridged by two(one) VO<sub>5</sub> groups in <b>1</b>(<b>2</b>), differing from those linked by SbO<sub>3</sub>/GeO<sub>4</sub>/SbO<sub>3</sub>-pyZnO<sub>4</sub> groups in the previously reported [Sb<sub>2</sub>Mo<sub>6</sub><sup>IV</sup>Mo<sub>2</sub><sup>V</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>32</sub>(OH)<sub>2</sub>py<sub>6</sub>]<sup>2–</sup> (<b>3</b>), [Ge<sub>2</sub>Mo<sub>6</sub><sup>IV</sup>Mo<sub>2</sub><sup>V</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>34</sub>(OH)<sub>2</sub>py<sub>6</sub>]<sup>4–</sup> (<b>4</b>), and [Sb<sub>2</sub>ZnMo<sub>6</sub><sup>IV</sup>Mo<sub>2</sub><sup>V</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>32</sub>(OH)<sub>2</sub>py<sub>7</sub>] (<b>5</b>), respectively. Multiple Mo<sup>IV</sup>···O//Sb<sup>III</sup> Lewis pairs in <b>1</b>–<b>3</b> construct well-organized Lewis catalysis fields (LCFs) featuring extensive Lewis acid–base synergistic interactions, which account for their excellent catalytic performance in heterogeneous hydrogen-transfer hydrogenation (HTH) reduction of nitrobenzene to aniline under mild conditions.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 25\",\"pages\":\"12560–12569\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-06-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00599\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00599","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Deeply Reduced Polyoxomolybdates Capped by Early Transition Metals with Catalytic Hydrogenation of Nitrobenzene
Deeply reduced polyoxometalates (POMs) capped by early transition metals, [V3IVMo6IVMo4VIO31py6]2– (1, py = pyridine) and [V2IVMo12IVMo8VIZn0.35H1.3+O54py12(HNMe2)2]2– (2), were prepared from solvothermal oxidative aggregations of [Mo3IVO2(O2CCH3)6(H2O)3]ZnCl4 and VO(acac)2 (acac = acetylacetonato). V3-capped Mo6IV-1 and V-capped Mo6IV-2 exhibit 12e-reduced POM structures characteristic of two [Mo3IVO4] incomplete cuboidal cluster units bridged by two(one) VO5 groups in 1(2), differing from those linked by SbO3/GeO4/SbO3-pyZnO4 groups in the previously reported [Sb2Mo6IVMo2VMo4VIO32(OH)2py6]2– (3), [Ge2Mo6IVMo2VMo4VIO34(OH)2py6]4– (4), and [Sb2ZnMo6IVMo2VMo4VIO32(OH)2py7] (5), respectively. Multiple MoIV···O//SbIII Lewis pairs in 1–3 construct well-organized Lewis catalysis fields (LCFs) featuring extensive Lewis acid–base synergistic interactions, which account for their excellent catalytic performance in heterogeneous hydrogen-transfer hydrogenation (HTH) reduction of nitrobenzene to aniline under mild conditions.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.