Iron diazoalkane chemistry: N-N bond hydrogenation and intramolecular C-H activation

被引：81

作者：

Bart, Suzanne C. ^{[1
]}

Bowman, Amanda C. ^{[1
]}

Lobkovsky, Emil ^{[1
]}

Chirik, Paul J. ^{[1
]}

机构：

[1] Cornell Univ, Dept Chem & Chem Biol, Baker Lab, Ithaca, NY 14853 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 23期

关键词：

D O I：

10.1021/ja070056u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Treatment of the intermediate spin ferrous bis(dinitrogen) complex, ((PDI)-P-iPr)Fe(N-2)(2) ((PDI)-P-iPr = 2,6-(2,6-Pr-i(2)-C6H3NCMe2)(2)C6H3N), with 1 equiv of N2CHSiMe3 afforded the corresponding iron diazoalkane compound, ((PDI)-P-iPr)Fe(N2CHSiMe3). Spectroscopic studies in conjunction with the metrical parameters from the solid-state structure support an intermediate spin ferrous complex with a doubly reduced chelate and a neutral diazoalkane ligand. In solution at 23 degrees C, ((PDI)-P-iPr)Fe(N2CHSiMe3) promotes the intramolecular C-H activation of an isopropyl aryl substituent with loss of SiMe4. Exposure of ((PDI)-P-iPr)Fe(N2CHSiMe3) to 1 atm of H-2 resulted in hydrogenative cleavage of the N-N and N-C bonds to yield ((PDI)-P-iPr)Fe(NH3) and SiMe4. Similar N-N bond cleavage chemistry was observed upon addition of hydrazine to ((PDI)-P-iPr)Fe(N-2)(2).

引用

页码：7212 / +

页数：3

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