Xinrui Ou, Fanji Kong, Kevin P. Quirion, Christopher K. Webber, Diane A. Dickie, Daniel H. Ess and T. Brent Gunnoe*,
{"title":"喹啉类Rh - Sb配合物的合成：抑制卤化物转移以获得Rh→Sb z型相互作用","authors":"Xinrui Ou, Fanji Kong, Kevin P. Quirion, Christopher K. Webber, Diane A. Dickie, Daniel H. Ess and T. Brent Gunnoe*, ","doi":"10.1021/acs.organomet.5c00187","DOIUrl":null,"url":null,"abstract":"<p >We report the synthesis of Rh–Sb complexes using high valent Sb ligands, Q<sub>3</sub>SbCl<sub>2</sub> (<b>1</b>, Q = 8-quinolinyl) and Q<sub>3</sub>SbF<sub>2</sub> (<b>2</b>), from the low valent Rh precursor [(CO)<sub>2</sub>Rh(μ-Cl)]<sub>2</sub> to afford the complexes [(κ<sup>4</sup>-Q<sub>3</sub>SbCl)Rh(CO)Cl][(CO)<sub>2</sub>RhCl<sub>2</sub>] (<b>3</b>) and (κ<sup>4</sup>-Q<sub>3</sub>SbF<sub>2</sub>)Rh(CO)Cl (<b>4</b>), respectively. The reaction of <b>1</b> with [(CO)<sub>2</sub>Rh(μ-Cl)]<sub>2</sub> results in the transfer of chloride from Sb to Rh to give the ion pair <b>3</b> with a Rh–Sb bond for the cation that, according to computational analysis, has some covalent character. Replacing Sb–Cl with Sb–F bonds (<i>i.e.</i>, compound <b>2</b>) inhibited halide transfer and allowed formation of <b>4</b> with a Rh→Sb interaction that has more Z-type character than the Rh–Sb bond for complex <b>3</b>. Molecular orbital and localized orbital bonding analyses are consistent with the proposed Rh→Sb interaction of <b>4</b> being more Z-type in character.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1639–1643"},"PeriodicalIF":2.9000,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00187","citationCount":"0","resultStr":"{\"title\":\"Synthesis of Quinoline-Based Rh–Sb Complexes: Inhibition of Halide Transfer to Access a Rh→Sb Z-Type Interaction\",\"authors\":\"Xinrui Ou, Fanji Kong, Kevin P. Quirion, Christopher K. Webber, Diane A. Dickie, Daniel H. Ess and T. Brent Gunnoe*, \",\"doi\":\"10.1021/acs.organomet.5c00187\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We report the synthesis of Rh–Sb complexes using high valent Sb ligands, Q<sub>3</sub>SbCl<sub>2</sub> (<b>1</b>, Q = 8-quinolinyl) and Q<sub>3</sub>SbF<sub>2</sub> (<b>2</b>), from the low valent Rh precursor [(CO)<sub>2</sub>Rh(μ-Cl)]<sub>2</sub> to afford the complexes [(κ<sup>4</sup>-Q<sub>3</sub>SbCl)Rh(CO)Cl][(CO)<sub>2</sub>RhCl<sub>2</sub>] (<b>3</b>) and (κ<sup>4</sup>-Q<sub>3</sub>SbF<sub>2</sub>)Rh(CO)Cl (<b>4</b>), respectively. The reaction of <b>1</b> with [(CO)<sub>2</sub>Rh(μ-Cl)]<sub>2</sub> results in the transfer of chloride from Sb to Rh to give the ion pair <b>3</b> with a Rh–Sb bond for the cation that, according to computational analysis, has some covalent character. Replacing Sb–Cl with Sb–F bonds (<i>i.e.</i>, compound <b>2</b>) inhibited halide transfer and allowed formation of <b>4</b> with a Rh→Sb interaction that has more Z-type character than the Rh–Sb bond for complex <b>3</b>. Molecular orbital and localized orbital bonding analyses are consistent with the proposed Rh→Sb interaction of <b>4</b> being more Z-type in character.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"44 15\",\"pages\":\"1639–1643\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00187\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00187\",\"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.5c00187","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Synthesis of Quinoline-Based Rh–Sb Complexes: Inhibition of Halide Transfer to Access a Rh→Sb Z-Type Interaction
We report the synthesis of Rh–Sb complexes using high valent Sb ligands, Q3SbCl2 (1, Q = 8-quinolinyl) and Q3SbF2 (2), from the low valent Rh precursor [(CO)2Rh(μ-Cl)]2 to afford the complexes [(κ4-Q3SbCl)Rh(CO)Cl][(CO)2RhCl2] (3) and (κ4-Q3SbF2)Rh(CO)Cl (4), respectively. The reaction of 1 with [(CO)2Rh(μ-Cl)]2 results in the transfer of chloride from Sb to Rh to give the ion pair 3 with a Rh–Sb bond for the cation that, according to computational analysis, has some covalent character. Replacing Sb–Cl with Sb–F bonds (i.e., compound 2) inhibited halide transfer and allowed formation of 4 with a Rh→Sb interaction that has more Z-type character than the Rh–Sb bond for complex 3. Molecular orbital and localized orbital bonding analyses are consistent with the proposed Rh→Sb interaction of 4 being more Z-type in character.
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.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
