Low-Spin Pseudotetrahedral Iron(I) Sites in Fe2(μ-S) Complexes

FeI 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 [(L3Fe)2(μ‐S)] complexes that were isolated and characterized in the low‐valent oxidation states FeIISFeII, FeIISFeI, and FeISFeI is described. This family of iron sulfides constitutes a unique redox series comprising three nearly isostructural but electronically distinct Fe2(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 FeII to FeI. The possibility of accessing low‐spin, pseudotetrahedral FeI sites compatible with S2− as a ligand was previously unknown. A new spin on FeI:FeI centers: A unique series of diiron [(L3Fe)2(μ‐S)] complexes were isolated and characterized in the low‐valent oxidation states FeIISFeII, FeIISFeI, and FeISFeI as nearly isostructural but electronically distinct species. Structural, magnetic, and spectroscopic studies indicated a transition of the pseudotetrahedral iron centers to low‐spin S=1/2 states upon reduction from FeII to FeI (see scheme).