Synthesis, electronic structure and reactivity of bis(imino)pyridine iron carbene complexes: evidence for a carbene radical
Synthesis, electronic structure and reactivity of bis(imino)pyridine iron carbene complexes: evidence for a carbene radical
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DOI：
10.1039/c3sc52450g
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发表时间：
2014-03-01
期刊：
影响因子：
8.4
通讯作者：
Chirik, Paul J.
中科院分区：
文献类型：
--
作者：
Russell, Sarah K.;Hoyt, Jordan M.;Chirik, Paul J.
研究了二取代重氮烷烃N2CPh2与一类双（亚）吡啶铁二氮配合物的反应性。对于该系列中最具立体保护的成员（(PDI)- p - ipr）Fe(N-2)(2) ((PDI)- p - ipr = 2,6-(2,6-(Pr2C6H3N)- pr -i=CMe)(2)C5H3N)，得到了S = 1铁重氮烷烃配合物并进行了结构表征。将2,6-芳基取代基缩小为乙基或甲基，可分离出二（亚胺）吡啶铁羰基配合物。磁测量建立了S = 1基态，在弱配体场中展示了铁碳烯的罕见例子。利用x射线衍射测量参数以及穆斯堡尔、XAS和计算数据确定了高自旋铁(s)化合物与氧化还原活性的双（亚）吡啶和卡宾自由基进行反铁磁偶联。
The reactivity of the disubstituted diazoalkane, N2CPh2 with a family of bis(imino)pyridine iron dinitrogen complexes was examined. For the most sterically protected member of the series, ((PDI)-P-iPr)Fe(N-2)(2) ((PDI)-P-iPr = 2,6-(2,6-(Pr2C6H3N)-Pr-i=CMe)(2)C5H3N), an S = 1 iron diazoalkane complex was obtained and structurally characterized. Reducing the size of the 2,6-aryl substituents to ethyl or methyl groups resulted in isolation of bis(imino)pyridine iron carbene complexes. Magnetic measurements established S = 1 ground states, demonstrating rare examples of iron carbenes in a weak ligand field. Electronic structure determination using metrical parameters from X-ray diffraction as well as Mossbauer, XAS and computational data established high-spin iron(s) compounds engaged in antiferromagnetic coupling with redox-active bis(imino)pyridine and carbene radicals.