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Synthesis and reactivity of the uranium phosphinidene metallocene [η<sup>5</sup>-1,3-(Me<sub>3</sub>Si)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sub>2</sub>U(P-2,4,6-<sup>i</sup>Pr<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)(OPMe<sub>3</sub>): influence of the coordinated Lewis base
12
Citations
119
References
2021
Year
This paper describes the synthesis and reactivity of [η<sup>5</sup>-1,3-(Me<sub>3</sub>Si)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sub>2</sub>U(P-2,4,6-<sup>i</sup>Pr<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)(OPMe<sub>3</sub>) (6) which is accessible from a ligand exchange reaction between [η<sup>5</sup>-1,3-(Me<sub>3</sub>Si)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sub>2</sub>U(P-2,4,6-<sup>i</sup>Pr<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)(OPPh<sub>3</sub>) (2) and Me<sub>3</sub>PO 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 <i>ortho</i>-dicyanobenzene <i>o</i>-C<sub>6</sub>H<sub>4</sub>(CN)<sub>2</sub> the zwitterionic species [η<sup>5</sup>-1,3-(Me<sub>3</sub>Si)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sub>2</sub>U[NHC(N){C<sub>6</sub>H<sub>4</sub>CP(2,4,6-<sup>i</sup>Pr<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)CH<sub>2</sub>PMe<sub>2</sub>O}] (13) is isolated in good yield. Moreover, 6 converts with Ph<sub>2</sub>S<sub>2</sub> to the uranium(III) phenylthiolate compound [η<sup>5</sup>-1,3-(Me<sub>3</sub>Si)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sub>2</sub>USPh(OPMe<sub>3</sub>) (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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