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Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex
Author(s) -
Lu Erli,
Cooper Oliver J.,
McMaster Jonathan,
Tuna Floriana,
McInnes Eric J. L.,
Lewis William,
Blake Alexander J.,
Liddle Stephen T.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201403892
Subject(s) - carbene , protonolysis , chemistry , uranium , heteroatom , pyridine , uranyl , medicinal chemistry , reactivity (psychology) , stereochemistry , ring (chemistry) , organic chemistry , catalysis , physics , ion , nuclear physics , medicine , alternative medicine , pathology
We report the uranium(VI) carbene imido oxo complex [U(BIPM TMS )(NMes)(O)(DMAP) 2 ] ( 5 , BIPM TMS =C(PPh 2 NSiMe 3 ) 2 ; Mes=2,4,6‐Me 3 C 6 H 2 ; DMAP=4‐(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two‐electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T‐shaped motif with respect to the carbene, which is consistent with an inverse trans ‐influence. Complex 5 reacts with tert ‐butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM TMS )(O) 2 (DMAP) 2 ] ( 6 ).