[AsCCAs]-Coordinated Rhenium Hydrides and Their Reactivities Toward Unsaturated Hydrocarbons, Heterocumulenes, and CO<sub>2</sub>
作者:Lukas Eberle、Franka Kreis、Carolin A. M. Stein、Jean-Marc Mörsdorf、Joachim Ballmann
DOI:10.1021/acs.inorgchem.3c00769
日期:2023.6.5
reaction of 3 with PhC≡CPh, ethylene, and CS2, monohydrides of the general formula [AsCCAs]Re(L)H with L = η2-PhC≡CPh (4), η2-H2C═CH2 (5), and η2-CS2 (6) were formed along with H2. In contrast, insertion products of the type [AsCCAs]Re(X)H2 (7–9) were obtained upon treatment of 3 with CyN═C═NCy, PhN═C═O, and Ph2C═C═O, while CO2 failed to react with 3 under identical reaction conditions. Given that several
具有中央炔烃和两个侧翼砷供体的 [AsCCAs] 配体被用于合成三氢铼络合物,而相应的磷配体被证明不太适合。详细检查了前三氢化物 [AsCCAs]ReH 3 ( 3 ) 的反应性,这表明可能会根据底物进入两个替代反应通道。在3与PhC≡CPh、乙烯和CS 2反应后,通式为[AsCCAs]Re(L)H的单氢化物,其中L = η 2 -PhC≡CPh ( 4 ), η 2 -H 2 C=CH 2 ( 5 ), 和 η 2 -CS2 ( 6 ) 与H 2一起形成。相反,[AsCCAs]Re(X)H 2 ( 7 –9) 类型的插入产物是在用 CyN=C=NCy、PhN=C=O 和 Ph 2 C=C=O 处理3后获得的,而CO 2在相同的反应条件下不能与3反应。鉴于文献中已经报道了CO 2和羰基氢化铼之间的几个生产性反应,通过分别引入 CO 和t BuNC 辅配体, 3进一步衍生化。这导致反式- [AsCCAs]ReH(CO)