Silyl-Phosphino-Carbene Complexes of Uranium(IV).

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(BIPMTMS )(Cl)(μ-Cl)2 Li(THF)2 ] (1, BIPMTMS =C(PPh2 NSiMe3 )2 ) into [U(BIPMTMS )(Cl){CH(Ph)(SiMe3 )}] (2), and addition of [Li{CH(SiMe3 )(PPh2 )}(THF)]/Me2 NCH2 CH2 NMe2 (TMEDA) gave [U{C(SiMe3 )(PPh2 )}(BIPMTMS )(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(SiMe3 )(PPh2 )}(BIPMTMS )(Cl)][Li(2,2,2-cryptand)] (4) or [U{C(SiMe3 )(PPh2 )}(BIPMTMS )(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.