A Multi-iron System Capable of Rapid N2 Formation and N2 Cleavage

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• 作者：K. Cory MacLeod ; David J. Vinyard ; Patrick L. Holland
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：July 23, 2014
• 年：2014
• 卷：136
• 期：29
• 页码：10226-10229
• 全文大小：255K
• ISSN：1520-5126

文摘

The six-electron oxidation of two nitrides to N₂ is a key step of ammonia synthesis and decomposition reactions on surfaces. In molecular complexes, nitride coupling has been observed with terminal nitrides, but not with bridging nitride complexes that more closely resemble catalytically important surface species. Further, nitride coupling has not been reported in systems where the nitrides are derived from N₂. Here, we show that a molecular diiron(II) diiron(III) bis(nitride) complex reacts with Lewis bases, leading to the rapid six-electron oxidation of two bridging nitrides to form N₂. Surprisingly, these mild reagents generate high yields of iron(I) products from the iron(II/III) starting material. This is the first molecular system that both breaks and forms the triple bond of N₂ at room temperature. These results highlight the ability of multi-iron species to decrease the energy barriers associated with the activation of strong bonds.