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Published June 2, 2014 | Accepted Version
Journal Article Open

Low-Spin Pseudotetrahedral Iron(I) Sites in Fe_2(μ-S) Complexes

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.

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