Low-Spin Pseudotetrahedral Iron(I) Sites in Fe_2(μ-S) Complexes
- Creators
- Anderson, John S.
- Peters, Jonas C.
Abstract
Fe^I centers in iron–sulfide complexes have little precedent in synthetic chemistry despite a growing interest in the possible role of unusually low valent iron in metalloenzymes that feature iron–sulfur clusters. A series of three diiron [(L_3Fe)_2(μ-S)] complexes that were isolated and characterized in the low-valent oxidation states Fe^(II) S Fe^(II), Fe^(II) S Fe^I, and Fe^I S Fe^I is described. This family of iron sulfides constitutes a unique redox series comprising three nearly isostructural but electronically distinct Fe_2(μ-S) species. Combined structural, magnetic, and spectroscopic studies provided strong evidence that the pseudotetrahedral iron centers undergo a transition to low-spin S=1/2 states upon reduction from Fe^(II) to Fe^I. The possibility of accessing low-spin, pseudotetrahedral Fe^I sites compatible with S^(2−) as a ligand was previously unknown.
Additional Information
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Article first published online: 17 Apr. 2014. Manuscript Received: 30 Jan 2014. This research was supported by the NIH (GM 070757). J.S.A. gratefully acknowledges a GRFP award from the NSF. Po-Heng Lin, Jay Winkler, Bruce Brunschwig, Harry Gray, and Dave Harris are thanked for helpful discussions.Attached Files
Accepted Version - nihms602979.pdf
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Additional details
- Alternative title
- Low-Spin Pseudotetrahedral Iron(I) Sites in Fe2(μ-S) Complexes
- PMCID
- PMC4155920
- Eprint ID
- 45241
- DOI
- 10.1002/anie.201401018
- Resolver ID
- CaltechAUTHORS:20140428-102317878
- GM 070757
- NIH
- NSF Graduate Research Fellowship
- Created
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2014-04-28Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field