前所未有的五配位铁（IV）酰亚胺基于酰亚胺R基团产生不同的自旋态。
Unprecedented Five-Coordinate Iron(IV) Imides Generate Divergent Spin States Based on the Imide R-Groups.
作者信息
Anneser Markus R, Elpitiya Gaya R, Townsend Jacob, Johnson Elizabeth J, Powers Xian B, DeJesus Joseph F, Vogiatzis Konstantinos D, Jenkins David M
机构信息
Department of Chemistry, University of Tennessee, Knoxville, TN, 37996, USA.
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 02138, USA.
出版信息
Angew Chem Int Ed Engl. 2019 Jun 11;58(24):8115-8118. doi: 10.1002/anie.201903132. Epub 2019 May 7.
Abstract
Three five-coordinate iron(IV) imide complexes have been synthesized and characterized. These novel structures have disparate spin states on the iron as a function of the R-group attached to the imide, with alkyl groups leading to low-spin diamagnetic (S=0) complexes and an aryl group leading to an intermediate-spin (S=1) complex. The different spin states lead to significant differences in the bonding about the iron center as well as the spectroscopic properties of these complexes. Mössbauer spectroscopy confirmed that all three imide complexes are in the iron(IV) oxidation state. The combination of diamagnetism and N labeling allowed for the first N NMR resonance recorded on an iron imide. Multi-reference calculations corroborate the experimental structural findings and suggest how the bonding is distinctly different on the imide ligand between the two spin states.
摘要
已合成并表征了三种五配位的铁（IV）酰亚胺配合物。这些新颖的结构在铁上具有不同的自旋态，这是连接到酰亚胺上的R基团的函数，烷基导致低自旋抗磁性（S = 0）配合物，芳基导致中间自旋（S = 1）配合物。不同的自旋态导致铁中心周围的键合以及这些配合物的光谱性质存在显著差异。穆斯堡尔光谱证实所有三种酰亚胺配合物均处于铁（IV）氧化态。抗磁性和N标记的结合使得首次记录到铁酰亚胺的N NMR共振。多参考计算证实了实验结构结果，并表明两种自旋态之间酰亚胺配体上的键合有明显不同。
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