Dongwei Wang, Yi Heng, Guohua Hou, Guofu Zi* and Marc D. Walter*,
{"title":"A Lewis-Base-Supported Terminal Thorium Imido Metallocene [{η5-1,2,4-(Me3Si)3C5H2}2Th═N(p-tolyl)(bipy)]: Synthesis and Reactivity","authors":"Dongwei Wang, Yi Heng, Guohua Hou, Guofu Zi* and Marc D. Walter*, ","doi":"10.1021/acs.organomet.4c0043110.1021/acs.organomet.4c00431","DOIUrl":null,"url":null,"abstract":"<p >Addition of <i>p</i>-tolylN<sub>3</sub> to a toluene solution of thorium bipyridyl metallocene [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th(bipy)] (<b>1</b>) causes N<sub>2</sub> evolution concomitant with the formation of Lewis-base-supported terminal thorium imido metallocene [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th═N(<i>p</i>-tolyl)(bipy)] (<b>2</b>). Complex <b>2</b> may initiate [2 + 2] or [2 + 1] cycloaddition reactions with internal alkynes PhC≡CPh and PhC≡CC≡CPh, thiobenzophenone Ph<sub>2</sub>CS, organic nitriles such as PhCH<sub>2</sub>CN and C<sub>6</sub>H<sub>11</sub>CN, and organic isonitriles such as 2,6-Me<sub>2</sub>PhNC and C<sub>6</sub>H<sub>11</sub>NC, yielding the amido complex [{η<sup>5</sup>-1-(CH<sub>2</sub>Me<sub>2</sub>Si)-2,4-(Me<sub>3</sub>Si)<sub>2</sub>C<sub>5</sub>H<sub>2</sub>}{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}Th{N(<i>p</i>-tolyl)C(Ph)═CH(Ph)}] (<b>3</b>), five-membered heterocyclic complex [{η<sup>5</sup>-1-(<i>p</i>-tolyl)NC(Ph)═CHCC(Ph)CH<sub>2</sub>SiMe<sub>2</sub>-2,4-(Me<sub>3</sub>Si)<sub>2</sub>C<sub>5</sub>H<sub>2</sub>}{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}Th] (<b>4</b>), disulfido complex [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th(S<sub>2</sub>CPh<sub>2</sub>)] (<b>6</b>), iminato complexes [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{η<sup>3</sup>-N(<i>p</i>-tolyl)C(CH<sub>2</sub>Ph)NH}(N═C═CHPh)] (<b>8</b>) and [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{η<sup>3</sup>-N(<i>p</i>-tolyl)C(C<sub>6</sub>H<sub>11</sub>)NH}{N═C═C(CH<sub>2</sub>)<sub>5</sub>}] (<b>9</b>), eight-membered heterocyclic complex [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{N(<i>p</i>-tolyl)C(═N-2,6-Me<sub>2</sub>Ph)C(H)═N(6-MePh-2-CH<sub>2</sub>)}] (<b>11</b>), and bis-amido complex [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{1-C<sub>6</sub>H<sub>11</sub>-2,2-(CH<sub>2</sub>)<sub>5</sub>-4-(<i>p</i>-tolyl)N-5-C<sub>6</sub>H<sub>11</sub>N-(1,3-C<sub>4</sub>HN<sub>2</sub>)}] (<b>12</b>), respectively. Moreover, with chlorosilane PhSiH<sub>2</sub>Cl complex <b>2</b> converts to thorium amido chloride complex [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th(Cl){N(<i>p</i>-tolyl)SiH<sub>2</sub>Ph}] (<b>13</b>), demonstrating that the thorium imido fragment may also act as a nucleophile. Nevertheless, complex <b>2</b> may also initiate deprotonation reactions as shown by its reactivity with the imine (<i>p</i>-tolyl)<sub>2</sub>C═NH and thiazole to yield the amido–iminato complex [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{NH(<i>p</i>-tolyl)}{N═C(<i>p</i>-tolyl)<sub>2</sub>}] (<b>14</b>) and amido thiazolyl compound [{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{NH(<i>p</i>-tolyl)}(C<sub>3</sub>H<sub>2</sub>NS)] (<b>15</b>), respectively. Last, but not the least, the cyclopentadienyl ligand [1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>]<sup>−</sup> of <b>2</b> can also be protonated by the terminal alkyne PhC≡CH, 1-indanone, and the nitrile Ph<sub>2</sub>CHCN to yield dimeric half-sandwich compounds [{{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}Th(C<sub>2</sub>Ph)(bipy)}<sub>2</sub>{μ-N(<i>p</i>-tolyl)}<sub>2</sub>] (<b>5</b>), [{{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}Th(1-O-CC<sub>8</sub>H<sub>7</sub>)(bipy)}<sub>2</sub>(μ-O)<sub>2</sub>] (<b>7</b>), and [{{η<sup>5</sup>-1,2,4-(Me<sub>3</sub>Si)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}Th(N═N═CPh<sub>2</sub>)(bipy)}<sub>2</sub>{μ-N(<i>p</i>-tolyl)}<sub>2</sub>] (<b>10</b>), respectively.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"207–223 207–223"},"PeriodicalIF":2.5000,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00431","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00431","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
Addition of p-tolylN3 to a toluene solution of thorium bipyridyl metallocene [{η5-1,2,4-(Me3Si)3C5H2}2Th(bipy)] (1) causes N2 evolution concomitant with the formation of Lewis-base-supported terminal thorium imido metallocene [{η5-1,2,4-(Me3Si)3C5H2}2Th═N(p-tolyl)(bipy)] (2). Complex 2 may initiate [2 + 2] or [2 + 1] cycloaddition reactions with internal alkynes PhC≡CPh and PhC≡CC≡CPh, thiobenzophenone Ph2CS, organic nitriles such as PhCH2CN and C6H11CN, and organic isonitriles such as 2,6-Me2PhNC and C6H11NC, yielding the amido complex [{η5-1-(CH2Me2Si)-2,4-(Me3Si)2C5H2}{η5-1,2,4-(Me3Si)3C5H2}Th{N(p-tolyl)C(Ph)═CH(Ph)}] (3), five-membered heterocyclic complex [{η5-1-(p-tolyl)NC(Ph)═CHCC(Ph)CH2SiMe2-2,4-(Me3Si)2C5H2}{η5-1,2,4-(Me3Si)3C5H2}Th] (4), disulfido complex [{η5-1,2,4-(Me3Si)3C5H2}2Th(S2CPh2)] (6), iminato complexes [{η5-1,2,4-(Me3Si)3C5H2}2Th{η3-N(p-tolyl)C(CH2Ph)NH}(N═C═CHPh)] (8) and [{η5-1,2,4-(Me3Si)3C5H2}2Th{η3-N(p-tolyl)C(C6H11)NH}{N═C═C(CH2)5}] (9), eight-membered heterocyclic complex [{η5-1,2,4-(Me3Si)3C5H2}2Th{N(p-tolyl)C(═N-2,6-Me2Ph)C(H)═N(6-MePh-2-CH2)}] (11), and bis-amido complex [{η5-1,2,4-(Me3Si)3C5H2}2Th{1-C6H11-2,2-(CH2)5-4-(p-tolyl)N-5-C6H11N-(1,3-C4HN2)}] (12), respectively. Moreover, with chlorosilane PhSiH2Cl complex 2 converts to thorium amido chloride complex [{η5-1,2,4-(Me3Si)3C5H2}2Th(Cl){N(p-tolyl)SiH2Ph}] (13), demonstrating that the thorium imido fragment may also act as a nucleophile. Nevertheless, complex 2 may also initiate deprotonation reactions as shown by its reactivity with the imine (p-tolyl)2C═NH and thiazole to yield the amido–iminato complex [{η5-1,2,4-(Me3Si)3C5H2}2Th{NH(p-tolyl)}{N═C(p-tolyl)2}] (14) and amido thiazolyl compound [{η5-1,2,4-(Me3Si)3C5H2}2Th{NH(p-tolyl)}(C3H2NS)] (15), respectively. Last, but not the least, the cyclopentadienyl ligand [1,2,4-(Me3Si)3C5H2]− of 2 can also be protonated by the terminal alkyne PhC≡CH, 1-indanone, and the nitrile Ph2CHCN to yield dimeric half-sandwich compounds [{{η5-1,2,4-(Me3Si)3C5H2}Th(C2Ph)(bipy)}2{μ-N(p-tolyl)}2] (5), [{{η5-1,2,4-(Me3Si)3C5H2}Th(1-O-CC8H7)(bipy)}2(μ-O)2] (7), and [{{η5-1,2,4-(Me3Si)3C5H2}Th(N═N═CPh2)(bipy)}2{μ-N(p-tolyl)}2] (10), respectively.
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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