{"title":"含有胂、砷化物和亚胂配体的锇和钌羰基团簇","authors":"","doi":"10.1016/j.ica.2024.122351","DOIUrl":null,"url":null,"abstract":"<div><p>The reactivity of trimetallic clusters [Os<sub>3</sub>(CO)<sub>10</sub>(NCMe)<sub>2</sub>], [M<sub>3</sub>(CO)<sub>10</sub>(µ-dppm)] [M = Os, Ru; dppm = bis(diphenylphosphino)methane] and [Os<sub>3</sub>(CO)<sub>8</sub>{µ<sub>3</sub>-Ph<sub>2</sub>PCH<sub>2</sub>PPh(C<sub>6</sub>H<sub>4</sub>)}(µ-H)] with triphenylarsine (AsPh<sub>3</sub>) has been investigated. The labile [Os<sub>3</sub>(CO)<sub>10</sub>(NCMe)<sub>2</sub>] reacts with AsPh<sub>3</sub> at room temperature to give 1,2-[Os<sub>3</sub>(CO)<sub>10</sub>(AsPh<sub>3</sub>)<sub>2</sub>] (<strong>1</strong>) in good yield. Thermolysis of <strong>1</strong> in refluxing toluene affords the known clusters [Os<sub>3</sub>(CO)<sub>11</sub>(AsPh<sub>3</sub>)] (<strong>2</strong>), [Os<sub>3</sub>(CO)<sub>9</sub>(µ-AsPh<sub>2</sub>)(µ<sub>3</sub>,η<sup>2</sup>-C<sub>6</sub>H<sub>4</sub>)(µ-H)] (<strong>3</strong>) and [Os<sub>3</sub>(CO)<sub>7</sub>(µ-AsPh<sub>2</sub>)<sub>2</sub>(µ<sub>3,</sub>η<sup>2</sup>-C<sub>6</sub>H<sub>4</sub>)] (<strong>4</strong>). Treatment of [Os<sub>3</sub>(CO)<sub>10</sub>(µ-dppm)] with AsPh<sub>3</sub> in refluxing toluene affords [Os<sub>3</sub>(CO)<sub>9</sub>(AsPh<sub>3</sub>)(µ-dppm)] (<strong>5</strong>) as the major product together with [Os<sub>3</sub>(CO)<sub>7</sub>(AsPh<sub>3</sub>){µ<sub>3</sub>-Ph<sub>2</sub>PCH<sub>2</sub>PPh(C<sub>6</sub>H<sub>4</sub>)}(µ-H)] (<strong>6</strong>). Control experiment shows that <strong>5</strong> is a precursor of <strong>6</strong> as the former converts to the latter under similar experimental conditions. The same reaction affords <strong>5</strong> as the sole product when it is carried out in refluxing benzene. Cluster <strong>5</strong> and <strong>6</strong> can also be obtained in similar yield by treating [Os<sub>3</sub>(CO)<sub>8</sub>{µ<sub>3</sub>-Ph<sub>2</sub>PCH<sub>2</sub>PPh(C<sub>6</sub>H<sub>4</sub>)}(µ-H)] with AsPh<sub>3</sub> at room temperature. On the other hand, the reaction of [Ru<sub>3</sub>(CO)<sub>10</sub>(µ-dppm)] with AsPh<sub>3</sub> in refluxing toluene furnishes only [Ru<sub>4</sub>(CO)<sub>8</sub>(µ-CO)(μ<sub>4</sub>-AsPh)(µ<sub>4</sub>,η<sup>2</sup>-C<sub>6</sub>H<sub>4</sub>)(µ-dppm)] (<strong>7</strong>) in low yield. Cluster <strong>7</strong> can also be obtained by heating [Ru<sub>3</sub>(CO)<sub>9</sub>(AsPh<sub>3</sub>)(µ-dppm)] in refluxing toluene. It contains a phenylarsinidene and a benzyne ligands that were formed by As<img>C bond cleavage during the reaction. The molecular structures of all the new products have been established by X-ray crystallography.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004420/pdfft?md5=f8ca26950a94971f3e0361e306867a80&pid=1-s2.0-S0020169324004420-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Osmium and ruthenium carbonyl clusters containing arsine, arsenide, and arsinidene ligands\",\"authors\":\"\",\"doi\":\"10.1016/j.ica.2024.122351\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The reactivity of trimetallic clusters [Os<sub>3</sub>(CO)<sub>10</sub>(NCMe)<sub>2</sub>], [M<sub>3</sub>(CO)<sub>10</sub>(µ-dppm)] [M = Os, Ru; dppm = bis(diphenylphosphino)methane] and [Os<sub>3</sub>(CO)<sub>8</sub>{µ<sub>3</sub>-Ph<sub>2</sub>PCH<sub>2</sub>PPh(C<sub>6</sub>H<sub>4</sub>)}(µ-H)] with triphenylarsine (AsPh<sub>3</sub>) has been investigated. The labile [Os<sub>3</sub>(CO)<sub>10</sub>(NCMe)<sub>2</sub>] reacts with AsPh<sub>3</sub> at room temperature to give 1,2-[Os<sub>3</sub>(CO)<sub>10</sub>(AsPh<sub>3</sub>)<sub>2</sub>] (<strong>1</strong>) in good yield. Thermolysis of <strong>1</strong> in refluxing toluene affords the known clusters [Os<sub>3</sub>(CO)<sub>11</sub>(AsPh<sub>3</sub>)] (<strong>2</strong>), [Os<sub>3</sub>(CO)<sub>9</sub>(µ-AsPh<sub>2</sub>)(µ<sub>3</sub>,η<sup>2</sup>-C<sub>6</sub>H<sub>4</sub>)(µ-H)] (<strong>3</strong>) and [Os<sub>3</sub>(CO)<sub>7</sub>(µ-AsPh<sub>2</sub>)<sub>2</sub>(µ<sub>3,</sub>η<sup>2</sup>-C<sub>6</sub>H<sub>4</sub>)] (<strong>4</strong>). Treatment of [Os<sub>3</sub>(CO)<sub>10</sub>(µ-dppm)] with AsPh<sub>3</sub> in refluxing toluene affords [Os<sub>3</sub>(CO)<sub>9</sub>(AsPh<sub>3</sub>)(µ-dppm)] (<strong>5</strong>) as the major product together with [Os<sub>3</sub>(CO)<sub>7</sub>(AsPh<sub>3</sub>){µ<sub>3</sub>-Ph<sub>2</sub>PCH<sub>2</sub>PPh(C<sub>6</sub>H<sub>4</sub>)}(µ-H)] (<strong>6</strong>). Control experiment shows that <strong>5</strong> is a precursor of <strong>6</strong> as the former converts to the latter under similar experimental conditions. The same reaction affords <strong>5</strong> as the sole product when it is carried out in refluxing benzene. Cluster <strong>5</strong> and <strong>6</strong> can also be obtained in similar yield by treating [Os<sub>3</sub>(CO)<sub>8</sub>{µ<sub>3</sub>-Ph<sub>2</sub>PCH<sub>2</sub>PPh(C<sub>6</sub>H<sub>4</sub>)}(µ-H)] with AsPh<sub>3</sub> at room temperature. On the other hand, the reaction of [Ru<sub>3</sub>(CO)<sub>10</sub>(µ-dppm)] with AsPh<sub>3</sub> in refluxing toluene furnishes only [Ru<sub>4</sub>(CO)<sub>8</sub>(µ-CO)(μ<sub>4</sub>-AsPh)(µ<sub>4</sub>,η<sup>2</sup>-C<sub>6</sub>H<sub>4</sub>)(µ-dppm)] (<strong>7</strong>) in low yield. Cluster <strong>7</strong> can also be obtained by heating [Ru<sub>3</sub>(CO)<sub>9</sub>(AsPh<sub>3</sub>)(µ-dppm)] in refluxing toluene. It contains a phenylarsinidene and a benzyne ligands that were formed by As<img>C bond cleavage during the reaction. The molecular structures of all the new products have been established by X-ray crystallography.</p></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004420/pdfft?md5=f8ca26950a94971f3e0361e306867a80&pid=1-s2.0-S0020169324004420-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004420\",\"RegionNum\":3,\"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":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004420","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Osmium and ruthenium carbonyl clusters containing arsine, arsenide, and arsinidene ligands
The reactivity of trimetallic clusters [Os3(CO)10(NCMe)2], [M3(CO)10(µ-dppm)] [M = Os, Ru; dppm = bis(diphenylphosphino)methane] and [Os3(CO)8{µ3-Ph2PCH2PPh(C6H4)}(µ-H)] with triphenylarsine (AsPh3) has been investigated. The labile [Os3(CO)10(NCMe)2] reacts with AsPh3 at room temperature to give 1,2-[Os3(CO)10(AsPh3)2] (1) in good yield. Thermolysis of 1 in refluxing toluene affords the known clusters [Os3(CO)11(AsPh3)] (2), [Os3(CO)9(µ-AsPh2)(µ3,η2-C6H4)(µ-H)] (3) and [Os3(CO)7(µ-AsPh2)2(µ3,η2-C6H4)] (4). Treatment of [Os3(CO)10(µ-dppm)] with AsPh3 in refluxing toluene affords [Os3(CO)9(AsPh3)(µ-dppm)] (5) as the major product together with [Os3(CO)7(AsPh3){µ3-Ph2PCH2PPh(C6H4)}(µ-H)] (6). Control experiment shows that 5 is a precursor of 6 as the former converts to the latter under similar experimental conditions. The same reaction affords 5 as the sole product when it is carried out in refluxing benzene. Cluster 5 and 6 can also be obtained in similar yield by treating [Os3(CO)8{µ3-Ph2PCH2PPh(C6H4)}(µ-H)] with AsPh3 at room temperature. On the other hand, the reaction of [Ru3(CO)10(µ-dppm)] with AsPh3 in refluxing toluene furnishes only [Ru4(CO)8(µ-CO)(μ4-AsPh)(µ4,η2-C6H4)(µ-dppm)] (7) in low yield. Cluster 7 can also be obtained by heating [Ru3(CO)9(AsPh3)(µ-dppm)] in refluxing toluene. It contains a phenylarsinidene and a benzyne ligands that were formed by AsC bond cleavage during the reaction. The molecular structures of all the new products have been established by X-ray crystallography.
期刊介绍：
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.
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