Zhang Lei, Hou Guohua, Zi Guofu, Ding Wanjian, Walter Marc D
Department of Chemistry, Beijing Normal University, Beijing 100875, China.
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.
Dalton Trans. 2017 Mar 14;46(11):3716-3728. doi: 10.1039/c7dt00396j.
The uranium metallacyclocumulene, [η-1,3-(MeC)CH]U(η-CPh) (2) was isolated by the reduction of [η-1,3-(MeC)CH]UCl (1) with potassium graphite (KC) in the presence of 1,4-diphenylbutadiyne (PhC[triple bond, length as m-dash]C-C[triple bond, length as m-dash]CPh) in good yield. Furthermore it was fully characterized including the determination of its molecular structure; and the reactivity of 2 towards various small unsaturated organic molecules was explored. For example, while complex 2 shows no reactivity with alkynes and 2,2'-bipyridine (bipy), it reacts as a nucleophile when exposed to carbodiimides, diazabutadienes, isothiocyanates, ketones, and pyridine derivatives, leading to five-, seven- or nine-membered heterometallacycles. In contrast, treatment of complex 2 with CS results in C[double bond, length as m-dash]S bond cleavage and forms the binuclear complex [η-1,3-(MeC)CH]U[μ-η:η-PhC[double bond, length as m-dash]C[double bond, length as m-dash]C(S)C(Ph)[double bond, length as m-dash]CS]U[η-1,3-(MeC)CH] (10). Density functional theory (DFT) studies complement the experimental study.
铀金属环累积烯烃[η-1,3-(MeC)CH]U(η-CPh) (2)是通过在1,4-二苯基丁二炔(PhC≡C-C≡CPh)存在下，用钾石墨(KC)还原[η-1,3-(MeC)CH]UCl (1)高产率分离得到的。此外，对其进行了全面表征，包括确定其分子结构；并探索了2对各种小不饱和有机分子的反应活性。例如，虽然配合物2与炔烃和2,2'-联吡啶(bipy)不发生反应，但当暴露于碳二亚胺、二氮杂丁二烯、异硫氰酸酯、酮和吡啶衍生物时，它作为亲核试剂反应，生成五元、七元或九元杂金属环。相比之下，用CS处理配合物2会导致C=S键断裂并形成双核配合物[η-1,3-(MeC)CH]U[μ-η:η-PhC=C=C(S)C(Ph)=CS]U[η-1,3-(MeC)CH] (10)。密度泛函理论(DFT)研究补充了实验研究。
