Wang Deqiang, Wang Shichun, Li Tongyu, Heng Yi, Hou Guohua, Zi Guofu, Walter Marc D
Department of Chemistry, Beijing Normal University, Beijing 100875, China.
Dalton Trans. 2021 Jun 22;50(24):8349-8363. doi: 10.1039/d1dt00742d.
The Lewis base supported terminal uranium phosphinidene metallocene [η5-1,3-(Me3C)2C5H3]2U([double bond, length as m-dash]P-2,4,6-iPr3C6H2)(OPMe3) (2) could be isolated from a salt metathesis reaction in toluene at ambient temperature between [η5-1,3-(Me3C)2C5H3]2U(Cl)Me (1) and 2,4,6-iPr3C6H2PHK in the presence of Me3PO, and its structure and reactivity were probed in detail. No reaction of 2 with internal alkynes was observed, but it reacts in the presence of various heterounsaturated molecules such as CS2, isothiocyanates, aldehydes, imines, diazenes, carbodiimides, nitriles, isonitriles, diazoalkane, and organic azides, forming carbodithioates, sulfidos, oxidos, metallaheterocycles, and imido complexes, in good yields. Moreover, on reaction with the diazoalkane derivative Me3SiCHN2 the pseudophosphinimido uranium(iii) complex [η5-1,3-(Me3C)2C5H3]2U(N[double bond, length as m-dash]P-2,4,6-iPr3C6H2)(OPMe3) (20) can be isolated in good yield.
路易斯碱支撑的末端铀磷烯金属茂[η5-1,3-(Me3C)2C5H3]2U([双键，长度为中划线]P-2,4,6-iPr3C6H2)(OPMe3) (2)可在室温下，于甲苯中通过盐复分解反应，由[η5-1,3-(Me3C)2C5H3]2U(Cl)Me (1)与2,4,6-iPr3C6H2PHK在Me3PO存在下制得，并对其结构和反应活性进行了详细研究。未观察到2与内炔烃发生反应，但在各种杂不饱和分子如CS2、异硫氰酸酯、醛、亚胺、重氮化合物、碳二亚胺、腈、异腈、重氮烷和有机叠氮化物存在下，它会发生反应，以良好的产率生成二硫代碳酸酯、硫化物、氧化物、金属杂环和亚胺基配合物。此外，与重氮烷衍生物Me3SiCHN2反应时，可高产率分离得到假磷亚胺基铀(iii)配合物[η5-1,3-(Me3C)2C5H3]2U(N[双键，长度为中划线]P-2,4,6-iPr3C6H2)(OPMe3) (20)。
