Yannick Schulte, Timo Freese, Christoph Wölper, Jan Schulte, Gebhard Haberhauer, Stephan Schulz
{"title":"单配位三态铋的合成及其反应性。","authors":"Yannick Schulte, Timo Freese, Christoph Wölper, Jan Schulte, Gebhard Haberhauer, Stephan Schulz","doi":"10.1002/anie.202508250","DOIUrl":null,"url":null,"abstract":"<p><p>The triplet bismuthinidene Ar*Bi (4) stabilized by a very bulky septiphenyl ligand (Ar* = 3,5-i-Pr<sub>2</sub>-2,6-(2,6-Me<sub>2</sub>-3,5-(2,6-i-Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)<sub>2</sub>-C<sub>6</sub>H)-C<sub>6</sub>H) was synthesized by dehydrogenation of in situ formed bismuth dihydride Ar*BiH<sub>2</sub> (3). Oxidative addition reactions of 4 with alkyl halides (MeI, EtBr, i-PrBr) yielded bismuthanes Ar*Bi(Me)I (5), Ar*Bi(Et)Br (6), and Ar*Bi(i-Pr)Br (7), which reacted with LiAlH<sub>4</sub> and LiAlD<sub>4</sub> to the thermally robust bismuth monohydrides Ar*Bi(R)H (R = Me 8, Et 10, i-Pr 12) and monodeuterides Ar*Bi(R)D (R = Me 9, Et 11, i-Pr 13). Ar*Bi(NMe<sub>2</sub>)<sub>2</sub> 1 and Ar*BiH<sub>2</sub> 3 were characterized in situ by <sup>1</sup>H NMR spectroscopy and sc-XRD (1), whereas the other compounds were characterized by heteronuclear NMR (<sup>1</sup>H/<sup>2</sup>H (D), <sup>13</sup>C) and IR spectroscopy, elemental analysis (Ar*-2, Ar*-3, Ar*-5, Ar*-7, Ar*I, Ar*H, 2, 4-7), as well as by UV-vis (4) and sc-XRD (Ar*-7, Ar*I, Ar*Li·Lit-Bu, Ar*H, 1, 2, 4, 12). Quantum chemical calculations revealed the triplet character of the bismuthinidine 4.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508250"},"PeriodicalIF":0.0000,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and Reactivity of a Mono-Coordinated Triplet Bismuthinidene.\",\"authors\":\"Yannick Schulte, Timo Freese, Christoph Wölper, Jan Schulte, Gebhard Haberhauer, Stephan Schulz\",\"doi\":\"10.1002/anie.202508250\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The triplet bismuthinidene Ar*Bi (4) stabilized by a very bulky septiphenyl ligand (Ar* = 3,5-i-Pr<sub>2</sub>-2,6-(2,6-Me<sub>2</sub>-3,5-(2,6-i-Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)<sub>2</sub>-C<sub>6</sub>H)-C<sub>6</sub>H) was synthesized by dehydrogenation of in situ formed bismuth dihydride Ar*BiH<sub>2</sub> (3). Oxidative addition reactions of 4 with alkyl halides (MeI, EtBr, i-PrBr) yielded bismuthanes Ar*Bi(Me)I (5), Ar*Bi(Et)Br (6), and Ar*Bi(i-Pr)Br (7), which reacted with LiAlH<sub>4</sub> and LiAlD<sub>4</sub> to the thermally robust bismuth monohydrides Ar*Bi(R)H (R = Me 8, Et 10, i-Pr 12) and monodeuterides Ar*Bi(R)D (R = Me 9, Et 11, i-Pr 13). Ar*Bi(NMe<sub>2</sub>)<sub>2</sub> 1 and Ar*BiH<sub>2</sub> 3 were characterized in situ by <sup>1</sup>H NMR spectroscopy and sc-XRD (1), whereas the other compounds were characterized by heteronuclear NMR (<sup>1</sup>H/<sup>2</sup>H (D), <sup>13</sup>C) and IR spectroscopy, elemental analysis (Ar*-2, Ar*-3, Ar*-5, Ar*-7, Ar*I, Ar*H, 2, 4-7), as well as by UV-vis (4) and sc-XRD (Ar*-7, Ar*I, Ar*Li·Lit-Bu, Ar*H, 1, 2, 4, 12). Quantum chemical calculations revealed the triplet character of the bismuthinidine 4.</p>\",\"PeriodicalId\":520556,\"journal\":{\"name\":\"Angewandte Chemie (International ed. in English)\",\"volume\":\" \",\"pages\":\"e202508250\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2025-07-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie (International ed. in English)\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1002/anie.202508250\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie (International ed. in English)","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/anie.202508250","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
摘要
用原位生成的二氢化铋Ar*BiH2(3)脱氢法制备了体积庞大的七苯基配体（Ar* = 3,5-i- pr2 -2,6-(2,6- me2 -3,5-(2,6-i- pr2c6h3)2- c6h)- c6h）稳定的铋铋Ar*Bi(4)三重态。4与烷基卤化物（MeI, EtBr, I - prbr）氧化加成反应生成Ar*Bi(Me)I (5), Ar*Bi(Et)Br(6)和Ar*Bi(I - pr)Br(7)，与LiAlH4和LiAlD4反应生成热稳定的铋单氢化物Ar*Bi(R)H （R = Me 8, Et 10, I - pr 12）和单氘化物Ar*Bi(R)D （R = Me 9, Et 11, I - pr 13）。Ar*Bi(NMe2)21和Ar*BiH23通过1H NMR和sc-XRD(1)进行了原位表征，其他化合物通过异核NMR （1H / 2H (D), 13C）和IR光谱，元素分析（Ar*-2, Ar*-3, Ar*-5, Ar*-7, Ar*I, Ar*H, 2,4 -7）以及UV-vis(4)和sc-XRD （Ar*-7, Ar*I, Ar*Li∙Li - bu, Ar*H, 1,2,4,12）进行了表征。量子化学计算揭示了铋锑4的三重态性质。
Synthesis and Reactivity of a Mono-Coordinated Triplet Bismuthinidene.
The triplet bismuthinidene Ar*Bi (4) stabilized by a very bulky septiphenyl ligand (Ar* = 3,5-i-Pr2-2,6-(2,6-Me2-3,5-(2,6-i-Pr2C6H3)2-C6H)-C6H) was synthesized by dehydrogenation of in situ formed bismuth dihydride Ar*BiH2 (3). Oxidative addition reactions of 4 with alkyl halides (MeI, EtBr, i-PrBr) yielded bismuthanes Ar*Bi(Me)I (5), Ar*Bi(Et)Br (6), and Ar*Bi(i-Pr)Br (7), which reacted with LiAlH4 and LiAlD4 to the thermally robust bismuth monohydrides Ar*Bi(R)H (R = Me 8, Et 10, i-Pr 12) and monodeuterides Ar*Bi(R)D (R = Me 9, Et 11, i-Pr 13). Ar*Bi(NMe2)2 1 and Ar*BiH2 3 were characterized in situ by 1H NMR spectroscopy and sc-XRD (1), whereas the other compounds were characterized by heteronuclear NMR (1H/2H (D), 13C) and IR spectroscopy, elemental analysis (Ar*-2, Ar*-3, Ar*-5, Ar*-7, Ar*I, Ar*H, 2, 4-7), as well as by UV-vis (4) and sc-XRD (Ar*-7, Ar*I, Ar*Li·Lit-Bu, Ar*H, 1, 2, 4, 12). Quantum chemical calculations revealed the triplet character of the bismuthinidine 4.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
