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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(BIPM(TMS))(Cl)(μ‐Cl)(2)Li(THF)(2)] (1, BIPM(TMS)=C(PPh(2)...

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Detalles Bibliográficos
Autores principales: Lu, Erli, Boronski, Josef T., Gregson, Matthew, Wooles, Ashley J., Liddle, Stephen T.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6001699/
https://www.ncbi.nlm.nih.gov/pubmed/29534326
http://dx.doi.org/10.1002/anie.201802080
Descripción
Sumario: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.