A Lewis Base Supported Terminal Uranium Phosphinidene Metallocene

A Lewis Base Supported Terminal Uranium Phosphinidene Metallocene
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路易斯碱负载端铀磷亚茂金属

DOI:
10.1021/acs.inorgchem.0c02363
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发表时间:
2020
影响因子:
4.6
通讯作者:
Walter Marc D.
Walter Marc D.
中科院分区:
化学2区
文献类型:
--
作者:
Wang Deqiang;Wang Shichun;Hou Guohua;Zi Guofu;Walter Marc D.

文献摘要

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从氯甲烷铀[η5- 1,3-(Me_3C)_2C_5 H_3]_2U(Cl)Me(4)与2,4,6-(Me_3C)_3C_6 H_2 PHK在甲苯中在Me_3 PO存在下的反应中分离得到一种刘易斯碱负载的末端铀次膦,[η5- 1,3-(Me_3C)_2C_5 H_3]_2U(OPMe_3)(5)。此外,还对磷化铀5与一系列小分子的反应性进行了全面的研究。由于空间位阻的原因,5与内炔没有反应性,但它很容易与各种小分子反应,产率很高,包括异硫氰酸酯、醛、亚胺、二氮烯、N-酰亚胺、腈、异腈和有机叠氮化物,产生硫化铀、氧化铀、金属杂环和酰亚胺络合物。
A Lewis base supported terminal uranium phosphinidene, [η5-1,3-(Me3C)2C5H3]2U(═P-2,4,6-tBu3C6H2)(OPMe3) (5), is isolated from the reaction of the uranium methyl chloride [η5-1,3-(Me3C)2C5H3]2U(Cl)Me (4) with 2,4,6-(Me3C)3C6H2PHK in toluene in the presence of Me3PO. Moreover, the reactivity of uranium phospinidene5toward a series of small molecules was comprehensively explored. While no reactivity of5with internal alkynes is observed attributed to steric hindrance, it readily reacts in good yields with various small molecules including isothiocyanates, aldehydes, imines, diazenes, carbodiimides, nitriles, isonitriles, and organic azides, yielding uranium sulfidos, oxidos, metallaheterocycles, and imido complexes.