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Uranium(III) coordination chemistry and oxidation in a flexible small-cavity macrocycle
journal contributionposted on 2023-05-18, 12:28 authored by Arnold, PL, Farnaby, JH, Michael GardinerMichael Gardiner, Love, JB
U(III) complexes of the conformationally flexible, small-cavity macrocycle trans-calixbenzenepyrrolide (L)2–, [U(L)X] (X = O-2,6-tBu2C6H3, N(SiMe3)2), have been synthesized from [U(L)BH4] and structurally characterized. These complexes show binding of the U(III) center in the bis(arene) pocket of the macrocycle, which flexes to accommodate the increase in the steric bulk of X, resulting in long U–X bonds to the ancillary ligands. Oxidation to the cationic U(IV) complex [U(L)X][B(C6F5)4] (X = BH4) results in ligand rearrangement to bind the smaller, harder cation in the bis(pyrrolide) pocket, in a conformation that has not been previously observed for (L)2–, with X located between the two ligand arene rings.
Department/SchoolSchool of Natural Sciences
PublisherAmer Chemical Soc
Place of publication1155 16Th St, Nw, Washington, USA, Dc, 20036
Rights statementCopyright 2015 American Chemical Society