The 1 : 1 reactions of uranium(iv) tetrakis(borohydride) with the sodium and potassium salts of the cyclobutadienyl anion [C(SiMe)] (Cb'''') produce the half-sandwich complexes [Na(12-crown-4)][U(η-Cb'''')(BH)] and [U(η-Cb'''')(μ-BH){K(THF)}]. In the 1 : 2 reaction of U(BH) with NaCb'''', formation of [U(η-Cb'''')(η-CH(SiMe)-κ-(CHSiMe)(BH))] 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.
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Department of Chemistry, School of Life Sciences, University of Sussex Brighton BN1 9QJ UK
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Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, BN1 9QR, UK.
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