Publication | Open Access
Silyl‐Phosphino‐Carbene Complexes of Uranium(IV)
52
Citations
85
References
2018
Year
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<sup>TMS</sup> )(Cl)(μ-Cl)<sub>2</sub> Li(THF)<sub>2</sub> ] (1, BIPM<sup>TMS</sup> =C(PPh<sub>2</sub> NSiMe<sub>3</sub> )<sub>2</sub> ) into [U(BIPM<sup>TMS</sup> )(Cl){CH(Ph)(SiMe<sub>3</sub> )}] (2), and addition of [Li{CH(SiMe<sub>3</sub> )(PPh<sub>2</sub> )}(THF)]/Me<sub>2</sub> NCH<sub>2</sub> CH<sub>2</sub> NMe<sub>2</sub> (TMEDA) gave [U{C(SiMe<sub>3</sub> )(PPh<sub>2</sub> )}(BIPM<sup>TMS</sup> )(μ-Cl)Li(TMEDA)(μ-TMEDA)<sub>0.5</sub> ]<sub>2</sub> (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<sub>3</sub> )(PPh<sub>2</sub> )}(BIPM<sup>TMS</sup> )(Cl)][Li(2,2,2-cryptand)] (4) or [U{C(SiMe<sub>3</sub> )(PPh<sub>2</sub> )}(BIPM<sup>TMS</sup> )(DMAP)<sub>2</sub> ] (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.
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