Synthesis and Characterization of a Novel Tetranuclear 5f Compound: A New Synthon for Exploring U(IV) Chemistry

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• 作者：Brian S. Newell ; Trevor C. Schwaab ; Matthew P. Shores
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：December 5, 2011
• 年：2011
• 卷：50
• 期：23
• 页码：12108-12115
• 全文大小：356K
• 年卷期：v.50,no.23(December 5, 2011)
• ISSN：1520-510X

文摘

In the course of structurally characterizing previously reported complexes based on the 1,2-bis(dimethylphosphino)ethane)) (dmpe) ligand ([(dmpe)<sub>2sub>UCl<sub>4sub>] (1) and [(dmpe)<sub>2sub>UMe<sub>4sub>] (2)), we find that adjusting the U/dmpe ratio leads to an unprecedented species. Whereas the use of two or three equivalents of dmpe relative to UCl<sub>4sub> produces 1 as a blue-green solid, the use of a 1:1 dmpe/UCl<sub>4sub> stoichiometry yields [(dmpe)<sub>4sub>U<sub>4sub>Cl<sub>16sub>]路2CH<sub>2sub>Cl<sub>2sub>路(3路2CH<sub>2sub>Cl<sub>2sub>) as a green solid. In turn, 3 is used to prepare a mixed-chelating ligand complex featuring the bidentate ligand 4,4鈥?dimethyl-2,2鈥?bipyridine (dmbpy), [(dmpe)(dmbpy)UCl<sub>4sub>] (4). The measured magnetic susceptibilities for 1鈥?b>4 trend toward nonmagnetic ground states at low temperatures.