Artem V. Kiselev , Ilya E. Nifant'ev , Alexander A. Vinogradov , Alexey A. Vinogradov , Vladimir V. Bagrov , Anna V. Afanaseva , Mikhail E. Minyaev , Pavel V. Ivchenko
{"title":"合理设计具有长 SiOSi 桥的ansa-heterocenes,作为辛-1-烯选择性二聚化的催化剂","authors":"Artem V. Kiselev , Ilya E. Nifant'ev , Alexander A. Vinogradov , Alexey A. Vinogradov , Vladimir V. Bagrov , Anna V. Afanaseva , Mikhail E. Minyaev , Pavel V. Ivchenko","doi":"10.1016/j.apcata.2024.119756","DOIUrl":null,"url":null,"abstract":"<div><p>Being activated by methylalumoxane ([Al]/[Zr] = 10), (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>ZrCl<sub>2</sub> (<strong>Zr1</strong>) and [(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>SiMe<sub>2</sub>)<sub>2</sub>O]ZrCl<sub>2</sub> (<strong>Zr2</strong>) catalyze selective dimerization of α-olefins with low productivity (turnover number TON ∼2000). Our previous research of heterocycle-fused <em>ansa</em>-zirconocenes revealed that SiMe<sub>2</sub>-bridged complexes catalyze polymerization of α-olefins, whereas CH<sub>2</sub>CH<sub>2</sub>-bridged complexes are high-performance oligomerization catalysts (TON ∼ 4∙10<sup>5</sup>). We proposed that further elongation of the bridge will allow obtaining dimerization catalysts. New –SiMe<sub>2</sub>OSiMe<sub>2</sub>– bridged <em>ansa</em>-zirconocenes <strong>Zr3</strong>–<strong>Zr11</strong> were synthesized and studied in oct-1-ene dimerization at 100 °C and [oct-1-ene]/[Zr] ratio of 3∙10<sup>4</sup>. In the absence of H<sub>2</sub> bis(5,6-dihydroindeno[2,1-<em>b</em>]indole) derivatives <strong>Zr8</strong> and <strong>Zr9</strong> demonstrated high activity and dimerization selectivity up to 94%. In the presence of H<sub>2</sub> symmetrical indenoindole complexes <strong>Zr5</strong>–<strong>Zr9</strong> appeared to be even more active, but up to 24% of hydrogenated oct-1-ene dimer HC16 was formed. Mixed-ligand complexes <strong>Zr10</strong> and <strong>Zr11</strong> catalyzed oct-1-ene dimerization with up to 99% selectivity without the formation of HC16 even in trace amounts.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7000,"publicationDate":"2024-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Rational design of ansa-heterocenes with a long SiOSi bridge as a catalysts for selective dimerization of oct-1-ene\",\"authors\":\"Artem V. Kiselev , Ilya E. Nifant'ev , Alexander A. Vinogradov , Alexey A. Vinogradov , Vladimir V. Bagrov , Anna V. Afanaseva , Mikhail E. Minyaev , Pavel V. Ivchenko\",\"doi\":\"10.1016/j.apcata.2024.119756\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Being activated by methylalumoxane ([Al]/[Zr] = 10), (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>ZrCl<sub>2</sub> (<strong>Zr1</strong>) and [(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>SiMe<sub>2</sub>)<sub>2</sub>O]ZrCl<sub>2</sub> (<strong>Zr2</strong>) catalyze selective dimerization of α-olefins with low productivity (turnover number TON ∼2000). Our previous research of heterocycle-fused <em>ansa</em>-zirconocenes revealed that SiMe<sub>2</sub>-bridged complexes catalyze polymerization of α-olefins, whereas CH<sub>2</sub>CH<sub>2</sub>-bridged complexes are high-performance oligomerization catalysts (TON ∼ 4∙10<sup>5</sup>). We proposed that further elongation of the bridge will allow obtaining dimerization catalysts. New –SiMe<sub>2</sub>OSiMe<sub>2</sub>– bridged <em>ansa</em>-zirconocenes <strong>Zr3</strong>–<strong>Zr11</strong> were synthesized and studied in oct-1-ene dimerization at 100 °C and [oct-1-ene]/[Zr] ratio of 3∙10<sup>4</sup>. In the absence of H<sub>2</sub> bis(5,6-dihydroindeno[2,1-<em>b</em>]indole) derivatives <strong>Zr8</strong> and <strong>Zr9</strong> demonstrated high activity and dimerization selectivity up to 94%. In the presence of H<sub>2</sub> symmetrical indenoindole complexes <strong>Zr5</strong>–<strong>Zr9</strong> appeared to be even more active, but up to 24% of hydrogenated oct-1-ene dimer HC16 was formed. 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Rational design of ansa-heterocenes with a long SiOSi bridge as a catalysts for selective dimerization of oct-1-ene
Being activated by methylalumoxane ([Al]/[Zr] = 10), (η5-C5H5)2ZrCl2 (Zr1) and [(η5-C5H4SiMe2)2O]ZrCl2 (Zr2) catalyze selective dimerization of α-olefins with low productivity (turnover number TON ∼2000). Our previous research of heterocycle-fused ansa-zirconocenes revealed that SiMe2-bridged complexes catalyze polymerization of α-olefins, whereas CH2CH2-bridged complexes are high-performance oligomerization catalysts (TON ∼ 4∙105). We proposed that further elongation of the bridge will allow obtaining dimerization catalysts. New –SiMe2OSiMe2– bridged ansa-zirconocenes Zr3–Zr11 were synthesized and studied in oct-1-ene dimerization at 100 °C and [oct-1-ene]/[Zr] ratio of 3∙104. In the absence of H2 bis(5,6-dihydroindeno[2,1-b]indole) derivatives Zr8 and Zr9 demonstrated high activity and dimerization selectivity up to 94%. In the presence of H2 symmetrical indenoindole complexes Zr5–Zr9 appeared to be even more active, but up to 24% of hydrogenated oct-1-ene dimer HC16 was formed. Mixed-ligand complexes Zr10 and Zr11 catalyzed oct-1-ene dimerization with up to 99% selectivity without the formation of HC16 even in trace amounts.
期刊介绍:
Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications.
Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.