Small-Molecule Activation Mediated by [η-1,3-(MeSi)CH]U(bipy).

The uranium bipyridyl metallocene, [η-1,3-(MeSi)CH]U(bipy) (), is readily accessible in good yield by adding potassium graphite (KC) to a mixture of [η-1,3-(MeSi)CH]UCl () and 2,2'-bipyridine. Compound was fully characterized and employed for small-molecule activation. It has been demonstrated that may serve as a synthon for [η-1,3-(MeSi)CH]U(II) fragment in the presence of PhE (E = S, Se), alkynes, and a variety of hetero-unsaturated molecules such as diazabutadienes, azine (PhC═N), -benzoquinone, pyridine -oxide, CS, isothiocyanates, and organic azides. However, upon exposure of to thio-ketone PhCS, aldehyde -MePhCHO, ketone PhCO, imine PhCH═NPh, azine (PhCH═N), and nitrile PhCN, it may also promote C-C coupling reactions forming [η-1,3-(MeSi)CH]U[(bipy)(PhCS)] (), [η-1,3-(MeSi)CH]U[(bipy)(-MePhCHO)] (), [η-1,3-(MeSi)CH]U[(bipy)(PhCO)] (), [η-1,3-(MeSi)CH]U[(bipy)(PhCHNPh)] (), [η-1,3-(MeSi)CH]U[(bipy)(PhCHNN═CHPh)] (), and [η-1,3-(MeSi)CH]U[(NCHC(Ph)NH)] (), 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-1,3-(MeSi)CH]U(I)(bipy) ().