Tuning Electronic Structure To Control Manganese Nitride Activation
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- 作者：Ryan M. Clarke ; Tim Storr
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：November 30, 2016
- 年：2016
- 卷：138
- 期：47
- 页码：15299-15302
- 全文大小：368K
- ISSN：1520-5126
文摘
Investigation of a series of oxidized nitridomanganese(V) salen complexes with different para ring substituents (R = CF3, tBu, and NMe2) demonstrates that nitride activation is dictated by remote ligand electronics. For R = CF3 and tBu, oxidation affords a Mn(VI) species and nitride activation, with dinitrogen homocoupling accelerated by the more electron-withdrawing CF3 substituent. Employing an electron-donating substituent (R = NMe2) results in a localized ligand radical species that is resistant to N coupling of the nitrides and is stable in solution at both 195 and 298 K.