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Small-Molecule Activation Mediated by [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(bipy)
32
Citations
111
References
2022
Year
The uranium bipyridyl 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(bipy) (<b>2</b>), is readily accessible in good yield by adding potassium graphite (KC<sub>8</sub>) to a mixture 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>UCl<sub>2</sub> (<b>1</b>) and 2,2'-bipyridine. Compound <b>2</b> was fully characterized and employed for small-molecule activation. It has been demonstrated that <b>2</b> may serve as a synthon for [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(II) fragment in the presence of Ph<sub>2</sub>E<sub>2</sub> (E = S, Se), alkynes, and a variety of hetero-unsaturated molecules such as diazabutadienes, azine (Ph<sub>2</sub>C═N)<sub>2</sub>, <i>o</i>-benzoquinone, pyridine <i>N</i>-oxide, CS<sub>2</sub>, isothiocyanates, and organic azides. However, upon exposure of <b>2</b> to thio-ketone Ph<sub>2</sub>CS, aldehyde <i>p</i>-MePhCHO, ketone Ph<sub>2</sub>CO, imine PhCH═NPh, azine (PhCH═N)<sub>2</sub>, and nitrile PhCN, it may also promote C-C coupling reactions forming [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[(bipy)(Ph<sub>2</sub>CS)] (<b>16</b>), [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[(bipy)(<i>p</i>-MePhCHO)] (<b>17</b>), [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[(bipy)(Ph<sub>2</sub>CO)] (<b>18</b>), [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[(bipy)(PhCHNPh)] (<b>19</b>), [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[(bipy)(PhCHNN═CHPh)] (<b>20</b>), and [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[(N<sub>2</sub>C<sub>10</sub>H<sub>7</sub>C(Ph)NH)] (<b>22</b>), respectively, in quantitative conversion. Furthermore, in the presence of CuI, a single-electron transfer (SET) process is observed to yield the uranium(III) iodide complex [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(I)(bipy) (<b>15</b>).
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