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Silyl‐Phosphino‐Carbene Complexes of Uranium(IV)
Author(s) -
Lu Erli,
Boronski Josef T.,
Gregson Matthew,
Wooles Ashley J.,
Liddle Stephen T.
Publication year - 2018
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.201802080
Subject(s) - chemistry , carbene , medicinal chemistry , uranium , actinide , silylation , stereochemistry , catalysis , organic chemistry , inorganic chemistry , materials science , metallurgy
Unprecedented silyl‐phosphino‐carbene complexes of uranium(IV) are presented, where before all covalent actinide–carbon double bonds were stabilised by phosphorus(V) substituents or restricted to matrix isolation experiments. Conversion of [U(BIPM TMS )(Cl)(μ‐Cl) 2 Li(THF) 2 ] ( 1 , BIPM TMS =C(PPh 2 NSiMe 3 ) 2 ) into [U(BIPM TMS )(Cl){CH(Ph)(SiMe 3 )}] ( 2 ), and addition of [Li{CH(SiMe 3 )(PPh 2 )}(THF)]/Me 2 NCH 2 CH 2 NMe 2 (TMEDA) gave [U{C(SiMe 3 )(PPh 2 )}(BIPM TMS )(μ‐Cl)Li(TMEDA)(μ‐TMEDA) 0.5 ] 2 ( 3 ) by α‐hydrogen abstraction. Addition of 2,2,2‐cryptand or two equivalents of 4‐N,N‐dimethylaminopyridine (DMAP) to 3 gave [U{C(SiMe 3 )(PPh 2 )}(BIPM TMS )(Cl)][Li(2,2,2‐cryptand)] ( 4 ) or [U{C(SiMe 3 )(PPh 2 )}(BIPM TMS )(DMAP) 2 ] ( 5 ). The characterisation data for 3 – 5 suggest that whilst there is evidence for 3‐centre P−C−U π‐bonding character, the U=C double bond component is dominant in each case. These U=C bonds are the closest to a true uranium alkylidene yet outside of matrix isolation experiments.