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

Shichun Wang; Yi Heng; Tongyu Li; Guohua Hou; Guofu Zi; Marc D. Walter

doi:10.1039/D1DT02149D

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†

Shichun Wang,^a Yi Heng,^a Tongyu Li,^a Guohua Hou,

^a Guofu Zi

*^a and Marc D. Walter

*^b

Author affiliations

* Corresponding authors

^a Department of Chemistry, Beijing Normal University, Beijing 100875, China
E-mail: gzi@bnu.edu.cn

^b Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany
E-mail: mwalter@tu-bs.de

Abstract

This paper describes the synthesis and reactivity of [η⁵-1,3-(Me₃Si)₂C₅H₃]₂U( [double bond, length as m-dash] P-2,4,6-ⁱPr₃C₆H₂)(OPMe₃) (6) which is accessible from a ligand exchange reaction between [η⁵-1,3-(Me₃Si)₂C₅H₃]₂U(P-2,4,6-ⁱPr₃C₆H₂)(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, nitriles, 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 [η⁵-1,3-(Me₃Si)₂C₅H₃]₂U[NHC(N){C₆H₄CP(2,4,6-ⁱPr₃C₆H₂)CH₂PMe₂O}] (13) is isolated in good yield. Moreover, 6 converts with Ph₂S₂ to the uranium(III) phenylthiolate compound [η⁵-1,3-(Me₃Si)₂C₅H₃]₂USPh(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.

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Article information

DOI: https://doi.org/10.1039/D1DT02149D
Article type: Paper
Submitted: 28 Jun 2021
Accepted: 27 Jul 2021
First published: 27 Jul 2021

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Dalton Trans., 2021,50, 12502-12516

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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

S. Wang, Y. Heng, T. Li, G. Hou, G. Zi and M. D. Walter, Dalton Trans., 2021, 50, 12502 DOI: 10.1039/D1DT02149D

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