Han Xianghao, Xiang Li, Lamsfus Carlos A, Mao Weiqing, Lu Erli, Maron Laurent, Leng Xuebing, Chen Yaofeng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077, Toulouse, France.
Chemistry. 2017 Oct 20;23(59):14728-14732. doi: 10.1002/chem.201703905. Epub 2017 Sep 22.
Dihydrogen is easily activated by a scandium terminal imido complex containing the weakly coordinated THF. The reaction proceeds through a 1,2-addition mechanism, which is distinct from the σ-bond metathesis mechanism reported to date for rare-earth metal-mediated H activation. This reaction yields a scandium terminal hydride, which is structurally well-characterized, being the first one to date. The reactivity of this hydride is reported with unsaturated substrates, further shedding light on the existence of the terminal hydride complex. Interestingly, the H activation can be reversible. DFT investigations further eludciate the mechanistic aspects of the reactivity of the scandium anilido-terminal hydride complex with PhNCS but also on the reversible H activation process.
二氢很容易被含有弱配位四氢呋喃的钪末端亚胺配合物活化。该反应通过1,2-加成机理进行，这与迄今为止报道的稀土金属介导的氢活化的σ键复分解机理不同。该反应生成了一种结构特征明确的钪末端氢化物，这是迄今为止的首例。报道了这种氢化物与不饱和底物的反应活性，进一步揭示了末端氢化物配合物的存在。有趣的是，氢活化可以是可逆的。密度泛函理论研究进一步阐明了钪苯胺基末端氢化物配合物与硫氰酸苯酯反应活性的机理方面，也阐明了可逆氢活化过程。
