Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

doi:10.1126/science.abd3054

GSTDTAP > 气候变化

DOI	10.1126/science.abd3054
	Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex
	Jorge L. Martinez; Sean A. Lutz; Hao Yang; Jiaze Xie; Joshua Telser; Brian M. Hoffman; Veronica Carta; Maren Pink; Yaroslav Losovyj; Jeremy M. Smith
	2020-10-16
发表期刊	Science
出版年	2020
英文摘要	The myriad ways that iron can interact with oxygen have been amply studied in biochemical and geochemical contexts. More recently, chemists have explored the extent to which nitrogen can likewise stabilize iron in high oxidation states. Martinez et al. now report that an iron center coordinated by carbene ligands can react with an organic azide to form a pentavalent bis(imido) complex with two Fe=N bonds. One-electron oxidation then accessed the Fe(VI) oxidation state. Both compounds were sufficiently stable for crystallographic characterization. Science , this issue p. [356][1] High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex ( 3 ) prepared by facile one-electron oxidation of an Fe(V) bis(imido) ( 2 ). Single-crystal x-ray diffraction of 2 and 3 revealed four-coordinate Fe centers with an unusual “seesaw” geometry. 57Fe Mössbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin ( S = 1/2) d3 Fe(V) configuration in 2 and a diamagnetic ( S = 0) d2 Fe(VI) configuration in 3 . Their shared seesaw geometry is electronically dictated by a balance of Fe-imido σ- and π-bonding interactions. [1]: /lookup/doi/10.1126/science.abd3054
领域	气候变化 ; 资源环境
URL	查看原文
引用统计
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/299348
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Jorge L. Martinez,Sean A. Lutz,Hao Yang,et al. Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex[J]. Science,2020.
APA	Jorge L. Martinez.,Sean A. Lutz.,Hao Yang.,Jiaze Xie.,Joshua Telser.,...&Jeremy M. Smith.(2020).Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex.Science.
MLA	Jorge L. Martinez,et al."Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex".Science (2020).