The Uranium(VI) Oxoazides [UOb>2b>(Nb>3b>)b>2b>⋅CHb>3b>CN], [(bipy)b>2b>(UOb>2b>)b>2b>(Nb>3b>)b>4b>], [(bipy)UOb>2b>(Nb>3b>)b>3b>]⁻, [UOb>2b>(Nb>3b>)b>4b>]²⁻, and [(UOb>2b>)b>2b>(Nb>3b>

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• 作者：Prof. Dr. Ralf Haiges ; Dr. Monica Vasiliu ; Prof. Dr. David A. Dixon and Prof. Dr. Karl O. Christe
• 刊名：Chemistry - A European Journal
• 出版年：2017
• 出版时间：January 12, 2017
• 年：2017
• 卷：23
• 期：3
• 页码：652-664
• 全文大小：3032K
• ISSN：1521-3765

文摘

The reaction between [UOb>2b>Fb>2b>] and an excess of Meb>3b>SiNb>3b> in acetonitrile solution results in fluoride–azide exchange and the uranium(VI) dioxodiazide adduct [UOb>2b>(Nb>3b>)b>2b>⋅CHb>3b>CN] was isolated in quantitative yield. The subsequent reaction of [UOb>2b>(Nb>3b>)b>2b>⋅CHb>3b>CN] with 2,2′-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy)b>2b>(UOb>2b>)b>2b>(Nb>3b>)b>4b>]. The triazido anion [(bipy)UOb>2b>(Nb>3b>)b>3b>]⁻ was obtained by the reaction of [UOb>2b>(Nb>3b>)b>2b>⋅CHb>3b>CN] with stoichiometric amounts of bipy and the ionic azide [PPhb>4b>][Nb>3b>]. The reaction of [UOb>2b>(Nb>3b>)b>2b>] with two equivalents of the [PPhb>4b>][Nb>3b>] resulted in the formation of the mononuclear tetraazido anion [UOb>2b>(Nb>3b>)b>4b>]²⁻ as well as the azido-bridged binuclear anion [(UOb>2b>)b>2b>(Nb>3b>)b>8b>]⁴⁻. The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy)b>2b>(UOb>2b>)b>2b>(Nb>3b>)b>4b>]⋅CHb>3b>CN, [PPhb>4b>][(bipy)UOb>2b>(Nb>3b>)b>3b>], [PPhb>4b>]b>2b>[UOb>2b>(Nb>3b>)b>4b>], [PPhb>4b>]b>2b>[UOb>2b>(Nb>3b>)b>4b>]⋅2CHb>3b>CN, and [PPhb>4b>]b>4b>[(UOb>2b>)b>2b>(Nb>3b>)b>8b>]⋅4CHb>3b>CN by their X-ray crystal structures.