Single‐Step Sulfur Insertions into Iron Carbide Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues. (8th December 2020)

• Record Type: Journal Article
• Authors: Joseph, Chris; Cobb, Caitlyn R.; Rose, Michael J.
• Is Part Of: Angewandte Chemie. Volume 133:Number 7(2021)
• Page Start: 3475
• Page End: 3479
• Publication Date: 2020-12-08
• Subjects: cluster compounds -- biomimetic synthesis -- carbides -- iron -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202011517
• Languages: English
• ISSNs: 0044-8249

Abstract

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 [Fe n (μ n ‐C)(CO) m ] x ( n =5, 6; m =15, 16; x =0, −2) with electrophilic sulfur sources (S2 Cl2, 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 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 [Fe5 (μ5 ‐C)(SC7 H7 )(CO)13 ] − . The strategy described herein provides a breakthrough towards developing syntheses of biomimetic iron‐sulfur‐carbide clusters like FeMoco. Abstract : At first glance, CO‐supported iron‐carbide clusters are an appealing synthetic starting point for modeling the carbide‐containing FeMoco cluster. However, these compounds have historically been uncontrollable towards traditional CO→S substitution methods. Demonstrated here is an approach utilizing unconventional electrophilic sulfur reagents to achieve carbide‐containing multi‐sulfide multi‐iron clusters.