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Uranium(iv) cyclobutadienyl sandwich compounds: synthesis, structure and chemical bonding

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Abstract

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.

Graphical abstract: Uranium(iv) cyclobutadienyl sandwich compounds: synthesis, structure and chemical bonding

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Article information


Submitted
19 Nov 2019
Accepted
11 Dec 2019
First published
11 Dec 2019

Chem. Commun., 2020, Advance Article
Article type
Communication

Uranium(IV) cyclobutadienyl sandwich compounds: synthesis, structure and chemical bonding

N. Tsoureas, A. Mansikkamäki and R. A. Layfield, Chem. Commun., 2020, Advance Article , DOI: 10.1039/C9CC09018E

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