Uranium(III) Complexes with Bulky Aryloxide Ligands Featuring Metal鈥揂rene Interactions and Their Reactivity Toward Nitrous Oxide

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• 作者：Sebastian M. Franke ; Ba L. Tran ; Frank W. Heinemann ; Wolfgang Hieringer ; Daniel J. Mindiola ; Karsten Meyer
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：September 16, 2013
• 年：2013
• 卷：52
• 期：18
• 页码：10552-10558
• 全文大小：347K
• 年卷期：v.52,no.18(September 16, 2013)
• ISSN：1520-510X

文摘

We report the synthesis and use of an easy-to-prepare, bulky, and robust aryloxide ligand starting from inexpensive precursor materials. Based on this aryloxide ligand, two reactive, coordinatively unsaturated U(III) complexes were prepared that are masked by a metal鈥揳rene interaction via 未-backbonding. Depending on solvent and uranium starting material, both a tetrahydrofuran (THF)-bound and Lewis-base-free U(III) precursor can easily be prepared on the multigram scale. The reaction of these trivalent uranium species with nitrous oxide, N₂O, was studied and an X-ray diffraction (XRD) study on single crystals of the product revealed the formation of a five-coordinate U(V) oxo complex with two different molecular geometries, namely, square pyramidal and trigonal bipyramidal.