{"title":"Highly regioselective anti-Markovnikov hydrosilylation of alkenes under mild conditions: Application of CCC-NHC pincer Rh complexes","authors":"Enock D. Amoateng, Evans Fosu, T. Keith Hollis","doi":"10.1016/j.jorganchem.2025.123579","DOIUrl":null,"url":null,"abstract":"<div><div>A highly selective hydrosilylation of alkenes at room temperature, catalyzed by well-defined CCC–NHC pincer Rh complexes, [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>Py] (<strong>1</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>(NHMe<sub>2</sub>)] (<strong>2</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>3</strong>), and [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)]<sub>2</sub> (<strong>4</strong>), (<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup> = 2-(1,3-bis(N-butylimidazol-2-ylidene)phenylene) has been achieved. The catalytic system exhibits excellent regioselectivity, affording anti-Markovnikov products in moderate to excellent conversions (48–100 %). Precatalyst [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>3</strong>) demonstrated the highest efficiency in promoting the anti-Markovnikov hydrosilylation of both aryl and alkyl alkenes with excellent selectivity (>99 %) when Et<sub>3</sub>SiH is used as silane source in acetonitrile. Notably, the system tolerates straight chain alkyl alkenes without inducing isomerization, a commonly encountered limitation with many hydrosilylation catalytic systems.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123579"},"PeriodicalIF":2.1000,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X25000737","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
A highly selective hydrosilylation of alkenes at room temperature, catalyzed by well-defined CCC–NHC pincer Rh complexes, [(BuCiCiCBu)RhCl2Py] (1), [(BuCiCiCBu)RhCl2(NHMe2)] (2), [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (3), and [(BuCiCiCBu)RhCl(µ-Cl)]2 (4), (BuCiCiCBu = 2-(1,3-bis(N-butylimidazol-2-ylidene)phenylene) has been achieved. The catalytic system exhibits excellent regioselectivity, affording anti-Markovnikov products in moderate to excellent conversions (48–100 %). Precatalyst [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (3) demonstrated the highest efficiency in promoting the anti-Markovnikov hydrosilylation of both aryl and alkyl alkenes with excellent selectivity (>99 %) when Et3SiH is used as silane source in acetonitrile. Notably, the system tolerates straight chain alkyl alkenes without inducing isomerization, a commonly encountered limitation with many hydrosilylation catalytic systems.
期刊介绍：
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.
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