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Low‐Spin Pseudotetrahedral Iron(I) Sites in Fe 2 (μ‐S) Complexes
Author(s) -
Anderson John S.,
Peters Jonas C.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201401018
Subject(s) - isostructural , chemistry , redox , iron sulfide , transition metal , crystallography , sulfide , inorganic chemistry , sulfur , ligand (biochemistry) , catalysis , crystal structure , organic chemistry , biochemistry , receptor
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 3 Fe) 2 (μ‐S)] complexes that were isolated and characterized in the low‐valent oxidation states Fe II SFe II , Fe II SFe I , and Fe I SFe 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.