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Title: Single‐Step Sulfur Insertions into Iron Carbide Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues
Abstract

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 [Fenn‐C)(CO)m]x(n=5,6;m=15,16;x=0,−2) with electrophilic sulfur sources (S2Cl2, S8) results in the formation of several μ4‐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 radicalS‐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 [Fe55‐C)(SC7H7)(CO)13]. The strategy described herein provides a breakthrough towards developing syntheses of biomimetic iron‐sulfur‐carbide clusters like FeMoco.

 
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Award ID(s):
1808311
PAR ID:
10204892
Author(s) / Creator(s):
 ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie
Volume:
133
Issue:
7
ISSN:
0044-8249
Page Range / eLocation ID:
p. 3475-3479
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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