In:
Chemistry – A European Journal, Wiley, Vol. 24, No. 4 ( 2018-01-19), p. 826-837
Kurzfassung:
Methyl benzoate, N , N ‐dimethylbenzamide, and benzophenone were reduced by U III [N(SiMe 3 ) 2 ] 3 resulting in uranium(IV) products. Reduction of benzophenone lead to U IV [OC ⋅ Ph 2 )][N(SiMe 3 ) 2 ] 3 , ( 1.1 ) which forms the dinuclear complex, [N(SiMe 3 ) 2 ] 3 U IV (OCPhPh‐CPh 2 O)U IV [N(SiMe 3 ) 2 ] 3 ( 1.2 ), through coupling of the ketyl radical species upon crystallization. Reaction of N , N ‐dimethylbenzamide with U III [N(SiMe 3 ) 2 ] 3 resulted in U IV [OC ⋅ (Ph)(NMe 2 )][N(SiMe 3 ) 2 ] 3 ( 2 ), a uranium(IV) compound and the first example of a charge‐separated amide radical. In the case of methyl benzoate, the reduction resulted in U IV (OMe)[N(SiMe 3 ) 2 ] 3 ( 3 ) and benzaldehyde as the reduced organic fragment. Compound 2 showed the ability to act as a uranium(III) synthon in its reactivity with trimethylsilyl azide, a reaction that yielded U V (=NSiMe 3 )[N(SiMe 3 ) 2 ] 3 . Additionally, 2 was reduced with potassium graphite resulting in [U(μ‐O)[O=C(NMe 2 )(Ph)][N(SiMe 3 ) 2 ] 2 ] 2 ( 4 ), a dinuclear uranium compound bridged by oxo ligands. Reduction of 2 in the presence of 15‐crown‐5 afforded isolation of the mono‐oxo compound, [(15‐crown‐5) 2 K][UO[N(SiMe 3 ) 2 ] 3 ] ( 5 ). The results expand the reduction capabilities of U III complexes and demonstrate a strategy for isolating novel metal‐stabilized radicals.
Materialart:
Online-Ressource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201703396
Sprache:
Englisch
Verlag:
Wiley
Publikationsdatum:
2018
ZDB Id:
1478547-X
