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1. Origin and consequences of non-stoichiometry in iron carbide Fe7C3

   https://doi.org/10.2138/am-2019-6672  

   Zhu, Feng ; Li, Jie ; Walker, David ; Liu, Jiachao ; Lai, Xiaojing ; Zhang, Dongzhou ( March 2019 , American Mineralogist)
2. Spectroscopic X-ray and Mössbauer Characterization of M 6 and M 5 Iron(Molybdenum)-Carbonyl Carbide Clusters: High Carbide-Iron Covalency Enhances Local Iron Site Electron Density Despite Cluster Oxidation

   https://doi.org/10.1021/acs.inorgchem.9b01870  

   McGale, Jeremy ; Cutsail, George E. ; Joseph, Chris ; Rose, Michael J. ; DeBeer, Serena ( September 2019 , Inorganic Chemistry)
3. Construction of Synthetic Models for Nitrogenase-Relevant NifB Biogenesis Intermediates and Iron-Carbide-Sulfide Clusters

   https://doi.org/10.3390/catal10111317  

   Joseph, Chris ; Shupp, John Patrick ; Cobb, Caitlyn R. ; Rose, Michael J. ( November 2020 , Catalysts)

   null (Ed.)

   The family of nitrogenase enzymes catalyzes the reduction of atmospheric dinitrogen (N2) to ammonia under remarkably benign conditions of temperature, pressure, and pH. Therefore, the development of synthetic complexes or materials that can similarly perform this reaction is of critical interest. The primary obstacle for obtaining realistic synthetic models of the active site iron-sulfur-carbide cluster (e.g., FeMoco) is the incorporation of a truly inorganic carbide. This review summarizes the present state of knowledge regarding biological and chemical (synthetic) incorporation of carbide into iron-sulfur clusters. This includes the Nif cluster of proteins and associated biochemistry involved in the endogenous biogenesis of FeMoco. We focus on the chemical (synthetic) incorporation portion of our own efforts to incorporate and modify C1 units in iron/sulfur clusters. We also highlight recent contributions from other research groups in the area toward C1 and/or inorganic carbide insertion. 

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

   https://doi.org/10.1002/anie.202011517  

   Joseph, Chris ; Cobb, Caitlyn R. ; Rose, Michael J. ( December 2020 , Angewandte Chemie International Edition)

   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 (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 [Fe₅(μ₅‐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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5. Single‐Step Sulfur Insertions into Iron Carbide Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues

   https://doi.org/10.1002/ange.202011517  

   Joseph, Chris ; Cobb, Caitlyn R. ; Rose, Michael J. ( December 2020 , Angewandte Chemie)

   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 (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 [Fe₅(μ₅‐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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