{"title":"咔唑基镧硼酸盐中 BH4- 阴离子的氢化物萃取","authors":"Lucas Winkler, Emma Stapf, Alexander Hinz","doi":"10.1021/acs.organomet.4c00095","DOIUrl":null,"url":null,"abstract":"Lanthanum borohydride complexes were synthesized by introducing a sterically demanding carbazole ligand (<sup>dtbp</sup>Cbz = 1,8-bis(3,5-di-<i>tert</i>-butylphenyl)-3,6-di-<i>tert</i>-butylcarbazolyl) into the coordination sphere of the lanthanide. Compound <b>1</b> (<sup>dtbp</sup>CbzLa(η<sup>3</sup>-BH<sub>4</sub>)<sub>2</sub>(THF)<sub>2</sub>) was obtained by a straightforward borohydride metathesis approach. We further investigated the coordination behavior toward abstraction of the solvent molecules. Removal of one THF molecule results in the dimeric structure of complex <b>2</b> ([<sup>dtbp</sup>CbzLa(BH<sub>4</sub>)<sub>2</sub>(THF)]<sub>2</sub>). However, the reaction with tris(pentafluorophenyl)borane does not lead to a second abstraction of THF. Instead, we observed borohydride decomposition and the formation of a π-coordinated lanthanum carbazolyl complex, (<sup>dtbp</sup>CbzBH<sub>3</sub>)La(BH<sub>4</sub>)[HB(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>](THF) (<b>3</b>).","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hydride Abstraction from a BH4– Anion in a Carbazolyl Lanthanum Boranate\",\"authors\":\"Lucas Winkler, Emma Stapf, Alexander Hinz\",\"doi\":\"10.1021/acs.organomet.4c00095\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Lanthanum borohydride complexes were synthesized by introducing a sterically demanding carbazole ligand (<sup>dtbp</sup>Cbz = 1,8-bis(3,5-di-<i>tert</i>-butylphenyl)-3,6-di-<i>tert</i>-butylcarbazolyl) into the coordination sphere of the lanthanide. Compound <b>1</b> (<sup>dtbp</sup>CbzLa(η<sup>3</sup>-BH<sub>4</sub>)<sub>2</sub>(THF)<sub>2</sub>) was obtained by a straightforward borohydride metathesis approach. We further investigated the coordination behavior toward abstraction of the solvent molecules. Removal of one THF molecule results in the dimeric structure of complex <b>2</b> ([<sup>dtbp</sup>CbzLa(BH<sub>4</sub>)<sub>2</sub>(THF)]<sub>2</sub>). However, the reaction with tris(pentafluorophenyl)borane does not lead to a second abstraction of THF. Instead, we observed borohydride decomposition and the formation of a π-coordinated lanthanum carbazolyl complex, (<sup>dtbp</sup>CbzBH<sub>3</sub>)La(BH<sub>4</sub>)[HB(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>](THF) (<b>3</b>).\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-04-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00095\",\"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://doi.org/10.1021/acs.organomet.4c00095","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Hydride Abstraction from a BH4– Anion in a Carbazolyl Lanthanum Boranate
Lanthanum borohydride complexes were synthesized by introducing a sterically demanding carbazole ligand (dtbpCbz = 1,8-bis(3,5-di-tert-butylphenyl)-3,6-di-tert-butylcarbazolyl) into the coordination sphere of the lanthanide. Compound 1 (dtbpCbzLa(η3-BH4)2(THF)2) was obtained by a straightforward borohydride metathesis approach. We further investigated the coordination behavior toward abstraction of the solvent molecules. Removal of one THF molecule results in the dimeric structure of complex 2 ([dtbpCbzLa(BH4)2(THF)]2). However, the reaction with tris(pentafluorophenyl)borane does not lead to a second abstraction of THF. Instead, we observed borohydride decomposition and the formation of a π-coordinated lanthanum carbazolyl complex, (dtbpCbzBH3)La(BH4)[HB(C6F5)3](THF) (3).
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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