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Abstract A pair of novel Fe‐alkynyl complexes, [FeIII(HMTI)(C2SiEt3)2]ClO4(2) and [FeII(HMTI)(C2SiEt3)(NCCH3)]ClO4(3), is described herein. Reaction of Fe(meso‐HMC)Cl(ClO4)]ClO4(1) with lithiated triethylsilylacetylene and subsequent exposure to oxygen yielded the bis‐alkynyl2containing the dehydrogenated tetraimine macrocycle (HMTI). Reduction of2by mossy zinc in acetonitrile yielded the mono‐alkynyl3. The structures of2and3were determined using single‐crystal X‐ray diffraction. Analysis of visible absorption and electrochemical data establishes the redox‐active nature of the HMTI macrocycle, and indicates significant interactions between the Fedπ and tetraimine π* orbitals. These deductions are further supported by density functional theory calculations.
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Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex
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 of2and3revealed 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) d3Fe(V) configuration in2and a diamagnetic (S= 0) d2Fe(VI) configuration in3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido σ- and π-bonding interactions.
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- PAR ID:
- 10200413
- Publisher / Repository:
- American Association for the Advancement of Science (AAAS)
- Date Published:
- Journal Name:
- Science
- Volume:
- 370
- Issue:
- 6514
- ISSN:
- 0036-8075
- Page Range / eLocation ID:
- p. 356-359
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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