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Single‐Step Sulfur Insertions into Iron Carbide Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues
Author(s) -
Joseph Chris,
Cobb Caitlyn R.,
Rose Michael J.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202011517
Subject(s) - sulfur , electrophile , chemistry , carbide , iron–sulfur cluster , biogenesis , cluster (spacecraft) , sulfide , crystallography , stereochemistry , combinatorial chemistry , organic chemistry , catalysis , biochemistry , computer science , programming language , gene , enzyme
The one‐step syntheses, X‐ray structures, and spectroscopic characterization of synthetic iron clusters, bearing either inorganic sulfides or thiolate with interstitial carbide motifs, are reported. Treatment of iron carbide carbonyl clusters [Fe n (μ n ‐C)(CO) m ] x ( n =5,6; m =15,16; x =0,−2) with electrophilic sulfur sources (S 2 Cl 2 , S 8 ) results in the formation of several μ 4 ‐S dimers of clusters, and moreover, iron‐sulfide‐(sulfocarbide) clusters. The core sulfocarbide unit {C−S} 4− serves as a structural model for a proposed intermediate in the radical S ‐adenosyl‐ L ‐methionine biogenesis of the M‐cluster. Furthermore, the electrophilic sulfur strategy has been extended to provide the first ever thiolato‐iron‐carbide complex: an analogous reaction with toluylsulfenyl chloride affords the cluster [Fe 5 (μ 5 ‐C)(SC 7 H 7 )(CO) 13 ] − . The strategy described herein provides a breakthrough towards developing syntheses of biomimetic iron‐sulfur‐carbide clusters like FeMoco.