0000000001298877
AUTHOR
Nikolaos Tsoureas
Isolation of a perfectly linear uranium(II) metallocene
Reduction of the uranium(III) metallocene [(eta(5)-(C5Pr5)-Pr-i)(2)UI] (1) with potassium graphite produces the "second-generation" uranocene [(eta(5)-(C5Pr5)-Pr-i)(2)U] (2), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground-state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f(3) 6d(1). Appreciable covalent contributions to the metal-ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbi…
Uranium( iv ) cyclobutadienyl sandwich compounds: synthesis, structure and chemical bonding
The 1 : 1 reactions of uranium(IV) tetrakis(borohydride) with the sodium and potassium salts of the cyclobutadienyl anion [C4(SiMe3)4]2− (Cb′′′′) produce the half-sandwich complexes [Na(12-crown-4)2][U(η4-Cb′′′′)(BH4)3] and [U(η4-Cb′′′′)(μ-BH4)3{K(THF)2}]2. In the 1 : 2 reaction of U(BH4)4 with Na2Cb′′′′, formation of [U(η4-Cb′′′′)(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(BH4))]− reveals that a Cb′′′′ ligand undergoes an intramolecular deprotonation, resulting in an allyl/tuck-in bonding mode. A computational study reveals that the uranium–Cb′′′′ bonding has an appreciable covalent component with contributions from the uranium 5f and 6d orbitals. peerReviewed
CCDC 1966630: Experimental Crystal Structure Determination
Related Article: Nikolaos Tsoureas, Akseli Mansikkamäki, Richard A. Layfield|2020|Chem.Commun.|56|944|doi:10.1039/C9CC09018E
CCDC 1966628: Experimental Crystal Structure Determination
Related Article: Nikolaos Tsoureas, Akseli Mansikkamäki, Richard A. Layfield|2020|Chem.Commun.|56|944|doi:10.1039/C9CC09018E
CCDC 1966629: Experimental Crystal Structure Determination
Related Article: Nikolaos Tsoureas, Akseli Mansikkamäki, Richard A. Layfield|2020|Chem.Commun.|56|944|doi:10.1039/C9CC09018E