Back to Search
Start Over
Small-Molecule Activation Mediated by [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U(bipy).
- Source :
-
Inorganic chemistry [Inorg Chem] 2022 Apr 25; Vol. 61 (16), pp. 6234-6251. Date of Electronic Publication: 2022 Apr 12. - Publication Year :
- 2022
-
Abstract
- The uranium bipyridyl metallocene, [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U(bipy) ( 2 ), is readily accessible in good yield by adding potassium graphite (KC <subscript>8</subscript> ) to a mixture of [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> UCl <subscript>2</subscript> ( 1 ) and 2,2'-bipyridine. Compound 2 was fully characterized and employed for small-molecule activation. It has been demonstrated that 2 may serve as a synthon for [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U(II) fragment in the presence of Ph <subscript>2</subscript> E <subscript>2</subscript> (E = S, Se), alkynes, and a variety of hetero-unsaturated molecules such as diazabutadienes, azine (Ph <subscript>2</subscript> C═N) <subscript>2</subscript> , o -benzoquinone, pyridine N -oxide, CS <subscript>2</subscript> , isothiocyanates, and organic azides. However, upon exposure of 2 to thio-ketone Ph <subscript>2</subscript> CS, aldehyde p -MePhCHO, ketone Ph <subscript>2</subscript> CO, imine PhCH═NPh, azine (PhCH═N) <subscript>2</subscript> , and nitrile PhCN, it may also promote C-C coupling reactions forming [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U[(bipy)(Ph <subscript>2</subscript> CS)] ( 16 ), [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U[(bipy)( p -MePhCHO)] ( 17 ), [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U[(bipy)(Ph <subscript>2</subscript> CO)] ( 18 ), [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U[(bipy)(PhCHNPh)] ( 19 ), [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U[(bipy)(PhCHNN═CHPh)] ( 20 ), and [η <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U[(N <subscript>2</subscript> C <subscript>10</subscript> H <subscript>7</subscript> C(Ph)NH)] ( 22 ), 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 <superscript>5</superscript> -1,3-(Me <subscript>3</subscript> Si) <subscript>2</subscript> C <subscript>5</subscript> H <subscript>3</subscript> ] <subscript>2</subscript> U(I)(bipy) ( 15 ).
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 61
- Issue :
- 16
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 35413191
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.2c00423