Synthesis of the (N2)3鈭?/sup> Radical from Y2+ and Its Protonolysis Reactivity To Form (N2H2)2鈭?/sup> via the Y[N(SiMe3)2]
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- 作者：Ming Fang ; David S. Lee ; Joseph W. Ziller ; Robert J. Doedens ; Jefferson E. Bates ; Filipp Furche ; William J. Evans
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：March 23, 2011
- 年：2011
- 卷：133
- 期：11
- 页码：3784-3787
- 全文大小：787K
- 年卷期：v.133,no.11(March 23, 2011)
- ISSN：1520-5126
文摘
Examination of the Y[N(SiMe3)2]3/KC8 reduction system that allowed isolation of the (N2)3鈭?/sup> radical has led to the first evidence of Y2+ in solution. The deep-blue solutions obtained from Y[N(SiMe3)2]3 and KC8 in THF at 鈭?5 掳C under argon have EPR spectra containing a doublet at giso = 1.976 with a 110 G hyperfine coupling constant. The solutions react with N2 to generate (N2)2鈭?/sup> and (N2)3鈭?/sup> complexes {[(Me3Si)2N]2(THF)Y}2(渭-畏2:畏2-N2) (1) and {[(Me3Si)2N]2(THF)Y}2(渭-畏2:畏2-N2)[K(THF)6] (2), respectively, and demonstrate that the Y[N(SiMe3)2]3/KC8 reaction can proceed through an Y2+ intermediate. The reactivity of (N2)3鈭?/sup> radical with proton sources was probed for the first time for comparison with the (N2)2鈭?/sup> and (N2)4鈭?/sup> chemistry. Complex 2 reacts with [Et3NH][BPh4] to form {[(Me3Si)2N]2(THF)Y}2(渭-N2H2), the first lanthanide (N2H2)2鈭?/sup> complex derived from dinitrogen, as well as 1 as a byproduct, consistent with radical disproportionation reactivity.