title: Cerium(III) and Uranium(IV) Complexes of the 2-Fluorophenyl Trimethylsilyl Amide Ligand: C-F → Ln/An Interactions that Modulate the Coordination Spheres of f-Block Elements.
abstract: 2-fluorophenyl trimethylsilyl amide, N(SiMe3)(C6H4F)(-) was shown to engage in stronger C-F → Ce(III) interactions than pentafluorophenyl trimethylsilyl amide, N(SiMe3)(C6F5)(-), through a comparative study of the Ce(III) model complexes Ce[N(SiMe3)(C6H4F)]3 (1-F1) and Ce[N(SiMe3)(C6F5)]3 (1-F5). The presence of multiple C-F → U(IV) interactions led to complexes 2-X (X = Cl, C≡CPh, OMe) with threefold geometries, featuring a trigonal pyramidal UN3Cl core in the solid-state structures. Density functional theory calculations were applied to 2-Cl to investigate the strength of the C-F → U(IV) interactions and the influence of such interactions on resulting geometries.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34 Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Haolin
authors.initials: H
authors.lastname: Yin
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34 Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34 Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter