Synthesis and reactivity of the uranium phosphinidene metallocene [η5-1,3-(Me3Si)2C5H3]2U(=P-2,4,6-iPr3C6H2)(OPMe3): influence of the coordinated Lewis base

被引：7

作者：

Wang, Shichun ^{[1
]}

Heng, Yi ^{[1
]}

Li, Tongyu ^{[1
]}

Hou, Guohua ^{[1
]}

Zi, Guofu ^{[1
]}

Walter, Marc D. ^{[2
]}

机构：

[1] Beijing Normal Univ, Dept Chem, Beijing 100875, Peoples R China

[2] Tech Univ Carolo Wilhelmina Braunschweig, Inst Arorgan & Analyt Chem, Hagenring 30, D-38106 Braunschweig, Germany

来源：

DALTON TRANSACTIONS | 2021年 / 50卷 / 36期

基金：

中国国家自然科学基金;

关键词：

H BOND ACTIVATION; SMALL-MOLECULE ACTIVATION; TERMINAL PHOSPHINIDENE; TRANSITION-METAL; RARE-EARTH; THORIUM-PHOSPHORUS; TITANIUM COMPLEXES; ACTINIDE COMPOUNDS; FORMING REACTIONS; 5F ORBITALS;

D O I：

10.1039/d1dt02149d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

This paper describes the synthesis and reactivity of (eta(5)-1,3-(Me3Si)(2)C3H3](2)U(=P-2,4,6-(Pr3C6H2)-Pr-i)(OPMe3) (6) which is accessible from a ligand exchange reaction between [eta(5)-1,3-(Me3Si)(2)C3H3](2)U (=P-2,4,6-(Pr3C6H2)-Pr-i)(OPPh3) (2) and Me3PO at ambient temperature. Phosphinidene 6 exhibits no reactivity towards internal alkynes, but readily reacts with various hetero-unsaturated molecules such as isothiocyanates, aldehydes, nitrites, isonitriles, and organic azides, forming uranium sulfido, oxido, imido, and uranaheterocyclic compounds. Nevertheless, with the bidentate ortho-dicyanobenzene o-C6H4(CN)(2) the zwitterionic species [eta(5)-1,3-(Me3Si)(2)C5H3](2)U[NHC(N)(C6H4CP(2,4,6-(Pr3C6H2)-Pr-i)CH2PMe2O)] (13) is isolated in good yield. Moreover, 6 converts with Ph2S2 to the uranium(m) phenylthiolate compound [eta(5)-1,3-(Me3Si)(2)C5H3](2)USPh(OPMe3) (7) in good isolated yield. Furthermore, the influence of the Lewis base on the reactivity of the uranium phosphinidene metallocenes has also been evaluated.

引用

页码：12502 / 12516

页数：15

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