Facile hydrogen atom abstraction and sulfide formation in a methyl-thiolate capped iron–sulfur–carbonyl cluster

Shupp, John Patrick; Rose, Michael J.

doi:10.1039/c9dt04098f

“…In a similar vein, the Holm group reported an iron‐sulfur cluster that incorporates a silyl‐nitride into the cluster core [19] . Two reports from our group demonstrated a series of interconversions between Fe 2 S 2 and Fe 3 S clusters in preliminary work for modeling carbon‐atom insertion as seen in FeMoco biogenesis (Figure 1), [20, 21] although ultimately carbide insertion proved unsuccessful.…”

Section: Figuresupporting

confidence: 55%

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

Joseph

¹

,

Cobb

²

,

Rose

³

2020

Angewandte Chemie

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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 [Fen(μn‐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 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)(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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“…Hydrogen sulfide (H 2 S) is downregulated in the DM heart, and H 2 S donor is cardioprotective and prevents DMCM ( 19 , 152 , 153 ). H 2 S donor treatment increases SLC7a11 in hyperglycemic myotubes, and SCL7a11 regulates cysteine import in the T2DM heart ( 9 , 154 ).…”

Section: Future Directionsmentioning

confidence: 99%

Ironing out the details: ferroptosis and its relevance to diabetic cardiomyopathy

Gawargi,

Mishra

2023

American Journal of Physiology-Regulatory, Integrative and Comp

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Ferroptosis is a newly identified myocardial cell death mechanism driven by iron-dependent lipid peroxidation. The presence of elevated intramyocardial lipid levels and excessive iron in diabetic patients suggest a predominant role of ferroptosis in diabetic cardiomyopathy. Since myocardial cell death is a precursor of heart failure and intensive glycemic control cannot abate the increased risk of heart failure in diabetic patients, targeting myocardial cell death via ferroptosis is a promising therapeutic avenue to prevent and/or treat diabetic cardiomyopathy. This review presents updated and comprehensive knowledge on mechanisms underpinning ferroptosis, clarifies several misconceptions about ferroptosis, emphasizes the importance of ferroptosis in diabetes-induced myocardial cell death, and offers valuable approaches to evaluate and target ferroptosis in the diabetic heart. Furthermore, basic concepts and ideas rendered in this review, including glutathione peroxidase-4-independent and mitochondrial mechanisms of ferroptosis, are also critical for investigating ferroptosis in other diabetic organs, as well as non-diabetic and metabolically compromised hearts.

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“…18 In a similar vein, the Holm group reported an iron-sulfur cluster that incorporates a silyl-nitride into the cluster core. 19 Two reports from our group demonstrated a series of interconversions between Fe 2 S 2 and Fe 3 S clusters in preliminary work for modeling carbon-atom insertion as seen in FeMoco biogenesis, 20,21 although ultimately carbide insertion proved unsuccessful. Despite this remarkable progress in understanding the synthetic, structural and functional aspects of iron, sulfur and carbon motifs, the synthetic challenge of incorporating both the biomimetic interstitial carbide and inorganic sulfide has proven difficult.…”

mentioning

confidence: 99%

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

Joseph

¹

,

Cobb

²

,

Rose

³

2020

Self Cite

View full text Add to dashboard Cite

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 [Fen(μn‐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 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)(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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Facile hydrogen atom abstraction and sulfide formation in a methyl-thiolate capped iron–sulfur–carbonyl cluster

Abstract: SAM mediated methyl transfer and subsequent hydrogen atom abstraction are key steps in the biogenesis of nitrogenase. A model system was utilized to demonstrate facile C–H abstraction from a methyl-thiolate containing iron–sulfur cluster with TEMPO.

Cited by 5 publications

References 22 publications

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

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

Ironing out the details: ferroptosis and its relevance to diabetic cardiomyopathy

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

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