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

ABSTRACT: 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)(?-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 )(?-Cl)Li(TMEDA)(?-TMEDA)0.5 ]2 (3) by ?-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 ?-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.

SUBMITTER: Lu E 

PROVIDER: S-EPMC6001699 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

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

Lu Erli E   Boronski Josef T JT   Gregson Matthew M   Wooles Ashley J AJ   Liddle Stephen T ST  

Angewandte Chemie (International ed. in English) 20180326 19

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>  ...[more]

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