Sourav Gayen, Sampad Shyamal, Faneesha Assanar and Sundargopal Ghosh*,
{"title":"锇硼烯丙基络合物：L(PPh3)(H)Os(ηn-B3H5L′2)]的结构和键合（L = H，Cp*；n = 5，3；L′ = C5H4NS，H）（Cp* = η5-C5Me5","authors":"Sourav Gayen, Sampad Shyamal, Faneesha Assanar and Sundargopal Ghosh*, ","doi":"10.1021/acs.organomet.4c0038510.1021/acs.organomet.4c00385","DOIUrl":null,"url":null,"abstract":"<p >Structures and bonding of various borallyl complexes stabilized in the coordination sphere of osmium have been demonstrated. For example, the Os-borallyl species [(PPh<sub>3</sub>)(H)<sub>2</sub>Os(η<sup>5</sup>-B<sub>3</sub>H<sub>5</sub>(C<sub>5</sub>H<sub>4</sub>NS)<sub>2</sub>)] (<b>2</b>) has been synthesized from the prolonged thermolysis of [(Ph<sub>3</sub>P)Os(κ<sup>2</sup>-<i>N,S</i>-(C<sub>5</sub>H<sub>4</sub>NS))<sub>2</sub>(κ<sup>1</sup>-<i>S</i>-(C<sub>5</sub>H<sub>4</sub>NS))] (<b>1</b>) with an excess amount of BH<sub>3</sub>·THF. The structural features of <b>2</b> suggest the presence of one linear triborane unit [B<sub>3</sub>H<sub>5</sub>(C<sub>5</sub>H<sub>4</sub>NS)<sub>2</sub>] which is stabilized in the coordination sphere of osmium through an η<sup>3</sup> bonding mode. Strikingly, the Os center in <b>2</b> possesses unique secondary interactions through two mercaptopyridinyl sulfur atoms, along with the primary η<sup>3</sup>-borallyl bonding. Furthermore, we have explored the reaction of [Cp*Os(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>4</b>) with BH<sub>3</sub>·THF that furnished another borallyl species, [Cp*(PPh<sub>3</sub>)(H)Os(η<sup>3</sup>-B<sub>3</sub>H<sub>7</sub>)] (<b>5</b>). Notably, species <b>2</b> and <b>5</b> are both structurally and electronically linked to <i>arachno</i>-B<sub>4</sub>H<sub>10</sub> in which the “hinge-tip” vertex is replaced by osmium. A detailed comparative analysis in combination with theoretical calculation offered valuable insights into the bonding scenarios in both borallyl species and aided us to assess their relative stability.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"43 22","pages":"2935–2943 2935–2943"},"PeriodicalIF":2.5000,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Osmium Borallyl Complexes: Structure and Bonding of [L(PPh3)(H)Os(ηn-B3H5L′2)], (L = H, Cp*; n = 5, 3; L′ = C5H4NS, H) (Cp* = η5-C5Me5)\",\"authors\":\"Sourav Gayen, Sampad Shyamal, Faneesha Assanar and Sundargopal Ghosh*, \",\"doi\":\"10.1021/acs.organomet.4c0038510.1021/acs.organomet.4c00385\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Structures and bonding of various borallyl complexes stabilized in the coordination sphere of osmium have been demonstrated. For example, the Os-borallyl species [(PPh<sub>3</sub>)(H)<sub>2</sub>Os(η<sup>5</sup>-B<sub>3</sub>H<sub>5</sub>(C<sub>5</sub>H<sub>4</sub>NS)<sub>2</sub>)] (<b>2</b>) has been synthesized from the prolonged thermolysis of [(Ph<sub>3</sub>P)Os(κ<sup>2</sup>-<i>N,S</i>-(C<sub>5</sub>H<sub>4</sub>NS))<sub>2</sub>(κ<sup>1</sup>-<i>S</i>-(C<sub>5</sub>H<sub>4</sub>NS))] (<b>1</b>) with an excess amount of BH<sub>3</sub>·THF. The structural features of <b>2</b> suggest the presence of one linear triborane unit [B<sub>3</sub>H<sub>5</sub>(C<sub>5</sub>H<sub>4</sub>NS)<sub>2</sub>] which is stabilized in the coordination sphere of osmium through an η<sup>3</sup> bonding mode. Strikingly, the Os center in <b>2</b> possesses unique secondary interactions through two mercaptopyridinyl sulfur atoms, along with the primary η<sup>3</sup>-borallyl bonding. Furthermore, we have explored the reaction of [Cp*Os(PPh<sub>3</sub>)<sub>2</sub>Cl] (<b>4</b>) with BH<sub>3</sub>·THF that furnished another borallyl species, [Cp*(PPh<sub>3</sub>)(H)Os(η<sup>3</sup>-B<sub>3</sub>H<sub>7</sub>)] (<b>5</b>). Notably, species <b>2</b> and <b>5</b> are both structurally and electronically linked to <i>arachno</i>-B<sub>4</sub>H<sub>10</sub> in which the “hinge-tip” vertex is replaced by osmium. A detailed comparative analysis in combination with theoretical calculation offered valuable insights into the bonding scenarios in both borallyl species and aided us to assess their relative stability.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"43 22\",\"pages\":\"2935–2943 2935–2943\"},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-11-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00385\",\"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":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00385","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 Borallyl Complexes: Structure and Bonding of [L(PPh3)(H)Os(ηn-B3H5L′2)], (L = H, Cp*; n = 5, 3; L′ = C5H4NS, H) (Cp* = η5-C5Me5)
Structures and bonding of various borallyl complexes stabilized in the coordination sphere of osmium have been demonstrated. For example, the Os-borallyl species [(PPh3)(H)2Os(η5-B3H5(C5H4NS)2)] (2) has been synthesized from the prolonged thermolysis of [(Ph3P)Os(κ2-N,S-(C5H4NS))2(κ1-S-(C5H4NS))] (1) with an excess amount of BH3·THF. The structural features of 2 suggest the presence of one linear triborane unit [B3H5(C5H4NS)2] which is stabilized in the coordination sphere of osmium through an η3 bonding mode. Strikingly, the Os center in 2 possesses unique secondary interactions through two mercaptopyridinyl sulfur atoms, along with the primary η3-borallyl bonding. Furthermore, we have explored the reaction of [Cp*Os(PPh3)2Cl] (4) with BH3·THF that furnished another borallyl species, [Cp*(PPh3)(H)Os(η3-B3H7)] (5). Notably, species 2 and 5 are both structurally and electronically linked to arachno-B4H10 in which the “hinge-tip” vertex is replaced by osmium. A detailed comparative analysis in combination with theoretical calculation offered valuable insights into the bonding scenarios in both borallyl species and aided us to assess their relative stability.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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