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1. 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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2. Nitrogen-enriched, Highly Pressurized Nebular Clouds Surrounding a Super Star Cluster at Cosmic Noon

   https://doi.org/10.3847/1538-4357/acf75c  

   Pascale, Massimo ; Dai, Liang ; McKee, Christopher F. ; Tsang, Benny T. -H. ( November 2023 , The Astrophysical Journal)

   Strong lensing offers a precious opportunity for studying the formation and early evolution of super star clusters that are rare in our cosmic backyard. The Sunburst Arc, a lensed Cosmic Noon galaxy, hosts a young super star cluster with escaping Lyman continuum radiation. Analyzing archival Hubble Space Telescope images and emission line data from Very Large Telescope/MUSE and X-shooter, we construct a physical model for the cluster and its surrounding photoionized nebula. We confirm that the cluster is ≲4 Myr old, is extremely massiveM_⋆∼ 10⁷M_⊙, and yet has a central component as compact as several parsecs, and we find a gas-phase metallicityZ= (0.22 ± 0.03)Z_⊙. The cluster is surrounded by ≳10⁵M_⊙of dense clouds that have been pressurized toP∼ 10⁹K cm⁻³by perhaps stellar radiation at within 10 pc. These should have large neutral columnsN_HI> 10^22.8cm⁻²to survive rapid ejection by radiation pressure. The clouds are likely dusty as they show gas-phase depletion of silicon, and may be conducive to secondary star formation ifN_HI> 10²⁴cm⁻²or if they sink farther toward the cluster center. Detecting strong [Niii]λλ1750,1752, we infer heavy nitrogen enrichment$\log (\mathrm{N}/\mathrm{O})=-{0.21}_{-0.11}^{+0.10}$. This requires efficiently retaining ≳500M_⊙of nitrogen in the high-pressure clouds from massive stars heavier than 60M_⊙up to 4 Myr. We suggest a physical origin of the high-pressure clouds from partial or complete condensation of slow massive star ejecta, which may have an important implication for the puzzle of multiple stellar populations in globular clusters.

    

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3. Metal‐Templated, Tight Loop Conformation of a Cys‐X‐Cys Biomimetic Assembles a Dimanganese Complex

   https://doi.org/10.1002/ange.201913259  

   Le, Trung ; Nguyen, Hao ; Perez, Lisa M. ; Darensbourg, Donald J. ; Darensbourg, Marcetta Y. ( January 2020 , Angewandte Chemie)

   With the goal of generating anionic analogues to MN₂S₂⋅Mn(CO)₃Br we introduced metallodithiolate ligands, MN₂S₂²⁻prepared from the Cys‐X‐Cys biomimetic, ema⁴⁻ligand (ema=N,N′‐ethylenebis(mercaptoacetamide); M=Ni^II, [V^IV≡O]²⁺and Fe^III) to Mn(CO)₅Br. An unexpected, remarkably stable dimanganese product, (H₂N₂(CH₂C=O(μ‐S))₂)[Mn(CO)₃]₂resulted from loss of M originally residing in the N₂S₂⁴⁻pocket, replaced by protonation at the amido nitrogens, generating H₂ema²⁻. Accordingly, the ema ligand has switched its coordination mode from an N₂S₂⁴⁻cavity holding a single metal, to a binucleating H₂ema²⁻with bridging sulfurs and carboxamide oxygens within Mn‐μ‐S‐CH₂‐C‐O, 5‐membered rings. In situ metal‐templating by zinc ions gives quantitative yields of the Mn₂product. By computational studies we compared the conformations of “linear” ema⁴⁻to ema⁴⁻frozen in the “tight‐loop” around single metals, and to the “looser” fold possible for H₂ema²⁻that is the optimal arrangement for binucleation. XRD molecular structures show extensive H‐bonding at the amido‐nitrogen protons in the solid state.

    

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4. Metal‐Templated, Tight Loop Conformation of a Cys‐X‐Cys Biomimetic Assembles a Dimanganese Complex

   https://doi.org/10.1002/anie.201913259  

   Le, Trung ; Nguyen, Hao ; Perez, Lisa M. ; Darensbourg, Donald J. ; Darensbourg, Marcetta Y. ( January 2020 , Angewandte Chemie International Edition)

   With the goal of generating anionic analogues to MN₂S₂⋅Mn(CO)₃Br we introduced metallodithiolate ligands, MN₂S₂²⁻prepared from the Cys‐X‐Cys biomimetic, ema⁴⁻ligand (ema=N,N′‐ethylenebis(mercaptoacetamide); M=Ni^II, [V^IV≡O]²⁺and Fe^III) to Mn(CO)₅Br. An unexpected, remarkably stable dimanganese product, (H₂N₂(CH₂C=O(μ‐S))₂)[Mn(CO)₃]₂resulted from loss of M originally residing in the N₂S₂⁴⁻pocket, replaced by protonation at the amido nitrogens, generating H₂ema²⁻. Accordingly, the ema ligand has switched its coordination mode from an N₂S₂⁴⁻cavity holding a single metal, to a binucleating H₂ema²⁻with bridging sulfurs and carboxamide oxygens within Mn‐μ‐S‐CH₂‐C‐O, 5‐membered rings. In situ metal‐templating by zinc ions gives quantitative yields of the Mn₂product. By computational studies we compared the conformations of “linear” ema⁴⁻to ema⁴⁻frozen in the “tight‐loop” around single metals, and to the “looser” fold possible for H₂ema²⁻that is the optimal arrangement for binucleation. XRD molecular structures show extensive H‐bonding at the amido‐nitrogen protons in the solid state.

    

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5. Thionitrite (SNO − ) and Perthionitrite (SSNO − ) are Simple Synthons for Nitrosylated Iron Sulfur Clusters

   https://doi.org/10.1002/anie.202204570  

   Sherbow, Tobias J. ; Fu, Wen ; Tao, Lizhi ; Zakharov, Lev N. ; Britt, R. David ; Pluth, Michael D. ( June 2022 , Angewandte Chemie International Edition)

   S/N crosstalk species derived from the interconnected reactivity of H₂S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe²⁺ions, such as those that are bioavailable in the labile iron pool (LIP), react with thionitrite (SNO⁻) and perthionitrite (SSNO⁻) to yield the dinitrosyl iron complex [Fe(NO)₂(S₅)]⁻. In the reaction of FeCl₂with SNO⁻we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl₂(NO)(SH)]⁻, which was characterized by X‐ray crystallography. We also show that [Fe(NO)₂(S₅)]⁻is a simple synthon for nitrosylated Fe−S clusters via its reduction with PPh₃to yield Roussin's Red Salt ([Fe₂S₂(NO)₄]²⁻), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe−S motifs.

    

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