Dongwei Wang, Yi Heng, Tongyu Li, Guofu Zi, Marc D. Walter
{"title":"Intrinsic Reactivity of [η5-1,3-(Me3C)2C5H3]2Th(bipy) toward Small Molecules","authors":"Dongwei Wang, Yi Heng, Tongyu Li, Guofu Zi, Marc D. Walter","doi":"10.1021/acs.organomet.4c00149","DOIUrl":null,"url":null,"abstract":"The reactivity of the thorium bipyridyl metallocene (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th(bipy) (<b>1</b>; Cp<sup>2<i>t</i>Bu</sup> = <i>η</i><sup>5</sup>-1,3-(Me<sub>3</sub>C)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>) toward a series of small molecules was explored, and the emerging reactivity pattern can be categorized: (1) It may act as a synthon for (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th(II) in contact with alkynes, diazabutadienes, ketazine (Ph<sub>2</sub>C═N)<sub>2</sub>, <i>o</i>-benzoquinone, carbodiimides, organic azides, isothiocyanates, elemental sulfur (S<sub>8</sub>) and selenium (Se), and Ph<sub>2</sub>S<sub>2</sub>. (2) It participates in C–C coupling reactions with ketones Ph<sub>2</sub>CO, (CH<sub>2</sub>)<sub>5</sub>CO, and 1-indanone, aldehydes <i>p</i>-MePhCHO and <i>p</i>-ClPhCHO, amidate PhCONH(<i>p</i>-tolyl), seleno-ketone (<i>p</i>-MeOPh)<sub>2</sub>CSe, imines PhCH═NPh and (<i>p</i>-tolyl)<sub>2</sub>C═NH, ketazine (PhCH═N)<sub>2</sub>, and nitriles PhCN, Me<sub>3</sub>CCN, C<sub>6</sub>H<sub>11</sub>CN and CH<sub>3</sub>CN, to form (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Ph<sub>2</sub>CO)] (<b>15</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)((CH<sub>2</sub>)<sub>5</sub>CO)] (<b>16</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(1-(C<sub>8</sub>H<sub>8</sub>)CO)] (<b>17</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-MePhCHO)] (<b>18</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-ClPhCHO)] (<b>19</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){PhCONH(<i>p</i>-tolyl)}] (<b>20</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){(<i>p</i>-MeOPh)<sub>2</sub>CSe}] (<b>21</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCHNPh)] (<b>22</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){(<i>p</i>-tolyl)<sub>2</sub>CNH}] (<b>23</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCHNN═CHPh)] (<b>24</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCN)] (<b>25</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Me<sub>3</sub>CCN)] (<b>26</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(C<sub>6</sub>H<sub>11</sub>CN)] (<b>27</b>), and (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(CH<sub>3</sub>CN)] (<b>28</b>), respectively. However, in the presence of benzyl nitrile PhCH<sub>2</sub>CN, the dimeric bis-amido complex {(Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[NHC(CH<sub>2</sub>Ph)C(Ph)C(C(Ph)CN)NH]}<sub>2</sub> (<b>29</b>) is isolated. (3) Isonitriles such as Me<sub>3</sub>CNC, Me<sub>3</sub>SiNC, and C<sub>6</sub>H<sub>11</sub>NC undergo C–N bond cleavage and C–C coupling to furnish the thorium isocyanido amido complexes (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(Me<sub>3</sub>C)bipy](NC) (<b>30</b>), (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(Me<sub>3</sub>Si)bipy](NC) (<b>31</b>), and (Cp<sup>2<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(C<sub>6</sub>H<sub>11</sub>)bipy](NC) (<b>32</b>), respectively. A comparison with related thorium bipyridyl metallocene derivatives shows that minor alternations in the supporting cyclopentadienyl ligands modulate the reactivity of these compounds.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-07-05","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.4c00149","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
The reactivity of the thorium bipyridyl metallocene (Cp2tBu)2Th(bipy) (1; Cp2tBu = η5-1,3-(Me3C)2C5H3) toward a series of small molecules was explored, and the emerging reactivity pattern can be categorized: (1) It may act as a synthon for (Cp2tBu)2Th(II) in contact with alkynes, diazabutadienes, ketazine (Ph2C═N)2, o-benzoquinone, carbodiimides, organic azides, isothiocyanates, elemental sulfur (S8) and selenium (Se), and Ph2S2. (2) It participates in C–C coupling reactions with ketones Ph2CO, (CH2)5CO, and 1-indanone, aldehydes p-MePhCHO and p-ClPhCHO, amidate PhCONH(p-tolyl), seleno-ketone (p-MeOPh)2CSe, imines PhCH═NPh and (p-tolyl)2C═NH, ketazine (PhCH═N)2, and nitriles PhCN, Me3CCN, C6H11CN and CH3CN, to form (Cp2tBu)2Th[(bipy)(Ph2CO)] (15), (Cp2tBu)2Th[(bipy)((CH2)5CO)] (16), (Cp2tBu)2Th[(bipy)(1-(C8H8)CO)] (17), (Cp2tBu)2Th[(bipy)(p-MePhCHO)] (18), (Cp2tBu)2Th[(bipy)(p-ClPhCHO)] (19), (Cp2tBu)2Th[(bipy){PhCONH(p-tolyl)}] (20), (Cp2tBu)2Th[(bipy){(p-MeOPh)2CSe}] (21), (Cp2tBu)2Th[(bipy)(PhCHNPh)] (22), (Cp2tBu)2Th[(bipy){(p-tolyl)2CNH}] (23), (Cp2tBu)2Th[(bipy)(PhCHNN═CHPh)] (24), (Cp2tBu)2Th[(bipy)(PhCN)] (25), (Cp2tBu)2Th[(bipy)(Me3CCN)] (26), (Cp2tBu)2Th[(bipy)(C6H11CN)] (27), and (Cp2tBu)2Th[(bipy)(CH3CN)] (28), respectively. However, in the presence of benzyl nitrile PhCH2CN, the dimeric bis-amido complex {(Cp2tBu)2Th[NHC(CH2Ph)C(Ph)C(C(Ph)CN)NH]}2 (29) is isolated. (3) Isonitriles such as Me3CNC, Me3SiNC, and C6H11NC undergo C–N bond cleavage and C–C coupling to furnish the thorium isocyanido amido complexes (Cp2tBu)2Th[4-(Me3C)bipy](NC) (30), (Cp2tBu)2Th[4-(Me3Si)bipy](NC) (31), and (Cp2tBu)2Th[4-(C6H11)bipy](NC) (32), respectively. A comparison with related thorium bipyridyl metallocene derivatives shows that minor alternations in the supporting cyclopentadienyl ligands modulate the reactivity of these compounds.
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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