Activation and functionalisation of carbon dioxide by bis-tris(pyrazolyl)borate-supported divalent samarium and trivalent lanthanide silylamide complexes†
Tajrian Chowdhury, Claire Wilson and Joy H. Farnaby
{"title":"Activation and functionalisation of carbon dioxide by bis-tris(pyrazolyl)borate-supported divalent samarium and trivalent lanthanide silylamide complexes†","authors":"Tajrian Chowdhury, Claire Wilson and Joy H. Farnaby","doi":"10.1039/D4DT01382D","DOIUrl":null,"url":null,"abstract":"<p >Synthesis and reactivity with carbon dioxide (CO<small><sub>2</sub></small>) of divalent samarium in the bis-tris(pyrazolyl)borate ligand environment has been reported. In addition, CO<small><sub>2</sub></small> activation and functionalisation by lanthanide silylamides in the bis-tris(pyrazolyl)borate ligand environment was demonstrated. Reduction of the Sm(<small>III</small>) precursor [Sm(Tp)<small><sub>2</sub></small>(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with KC<small><sub>8</sub></small> yielded the insoluble Sm(<small>II</small>) multi-metallic coordination polymer [{Sm(Tp)<small><sub>2</sub></small>}<small><sub><em>n</em></sub></small>] <strong>1-Sm</strong>. Addition of 1,2-dimethoxyethane (DME) to <strong>1-Sm</strong> enabled isolation of the monomeric complex [Sm(Tp)<small><sub>2</sub></small>(DME)] <strong>1-Sm(DME)</strong>. Complex <strong>1-Sm(DME)</strong> reduced CO<small><sub>2</sub></small> to yield the oxalate-bridged dimeric Sm(<small>III</small>) complex [{Sm(Tp)<small><sub>2</sub></small>}<small><sub>2</sub></small>(μ-η<small><sup>2</sup></small>:η<small><sup>2</sup></small>-O<small><sub>2</sub></small>CCO<small><sub>2</sub></small>)] <strong>2-Sm</strong>. The reactions of heteroleptic Ln(<small>III</small>) silylamide complexes [Ln(Tp)<small><sub>2</sub></small>(N′′)] (Ln = Y, Sm; N′′ = N(SiMe<small><sub>3</sub></small>)<small><sub>2</sub></small>) with CO<small><sub>2</sub></small> yielded monomeric Ln(<small>III</small>) silyloxides [Ln(Tp)<small><sub>2</sub></small>(OSiMe<small><sub>3</sub></small>)] <strong>3-Ln</strong> and trimethylsilyl isocyanate (O<img>C<img>NSiMe<small><sub>3</sub></small>). Complexes <strong>3-Ln</strong> are the first crystallographically characterised examples of Ln(<small>III</small>)–OSiMe<small><sub>3</sub></small> bonds accessed <em>via</em> CO<small><sub>2</sub></small> activation and functionalisation. Full characterisation data are presented for all complexes, including solid-state molecular structure determination by single-crystal X-ray diffraction.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/dt/d4dt01382d?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt01382d","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Synthesis and reactivity with carbon dioxide (CO2) of divalent samarium in the bis-tris(pyrazolyl)borate ligand environment has been reported. In addition, CO2 activation and functionalisation by lanthanide silylamides in the bis-tris(pyrazolyl)borate ligand environment was demonstrated. Reduction of the Sm(III) precursor [Sm(Tp)2(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with KC8 yielded the insoluble Sm(II) multi-metallic coordination polymer [{Sm(Tp)2}n] 1-Sm. Addition of 1,2-dimethoxyethane (DME) to 1-Sm enabled isolation of the monomeric complex [Sm(Tp)2(DME)] 1-Sm(DME). Complex 1-Sm(DME) reduced CO2 to yield the oxalate-bridged dimeric Sm(III) complex [{Sm(Tp)2}2(μ-η2:η2-O2CCO2)] 2-Sm. The reactions of heteroleptic Ln(III) silylamide complexes [Ln(Tp)2(N′′)] (Ln = Y, Sm; N′′ = N(SiMe3)2) with CO2 yielded monomeric Ln(III) silyloxides [Ln(Tp)2(OSiMe3)] 3-Ln and trimethylsilyl isocyanate (OCNSiMe3). Complexes 3-Ln are the first crystallographically characterised examples of Ln(III)–OSiMe3 bonds accessed via CO2 activation and functionalisation. Full characterisation data are presented for all complexes, including solid-state molecular structure determination by single-crystal X-ray diffraction.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.