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1. 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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2. 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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3. The extraplanar type II supernova ASASSN-14jb in the nearby edge-on galaxy ESO 467-G051

   https://doi.org/10.1051/0004-6361/201834972  

   Meza, Nicolás ; Prieto, J. L. ; Clocchiatti, A. ; Galbany, L. ; Anderson, J. P. ; Falco, E. ; Kochanek, C. S. ; Kuncarayakti, H. ; Sánchez, S. F. ; Brimacombe, J. ; et al ( September 2019 , Astronomy & Astrophysics)

   We present optical photometry and spectroscopy of the Type II supernova ASASSN-14jb, together with Very Large Telescope (VLT) Multi Unit Spectroscopic Explorer (MUSE) integral field observations of its host galaxy and a nebular-phase spectrum. This supernova, in the nearby galaxy ESO 467-G051 ( z  = 0.006), was discovered and followed-up by the all-sky automated survey for supernovae (ASAS-SN). We obtained well-sampled las cumbres network (LCOGTN) B V g r i and Swift w 2 m 1 w 1 u b v optical, near-UV/optical light curves, and several optical spectra in the early photospheric phases. The transient ASASSN-14jb exploded ∼2 kpc above the star-forming disk of ESO 467-G051, an edge-on disk galaxy. The large projected distance from the disk of the supernova position and the non-detection of any H II region in a 1.4 kpc radius in projection are in conflict with the standard environment of core-collapse supernova progenitors and suggests the possible scenario that the progenitor received a kick in a binary interaction. We present analysis of the optical light curves and spectra, from which we derived a distance of 25 ± 2 Mpc using state-of-the-art empirical methods for Type II SNe, physical properties of the SN explosion ( 56 Ni mass, explosion energy, and ejected mass), and properties of the progenitor; namely the progenitor radius, mass, and metallicity. Our analysis yields a 56 Ni mass of 0.0210  ±  0.0025  M ⊙ , an explosion energy of ≈0.25 × 10 51 ergs, and an ejected mass of ≈6  M ⊙ . We also constrained the progenitor radius to be R *  = 580  ±  28  R ⊙ which seems to be consistent with the sub-Solar metallicity of 0.3  ±  0.1  Z ⊙ derived from the supernova Fe II λ 5018 line. The nebular spectrum constrains strongly the progenitor mass to be in the range 10–12 M ⊙ . From the Spitzer data archive we detect ASASSN-14jb ≈330 days past explosion and we derived a total dust mass of 10 −4   M ⊙ from the 3.6 μ m and 4.5 μ m photometry. Using the F U V , N U V , B V g r i , K s , 3.6 μ m, and 4.5 μ m total magnitudes for the host galaxy, we fit stellar population synthesis models, which give an estimate of M *  ≈ 1 × 10 9   M ⊙ , an age of 3.2 Gyr, and a SFR ≈0.07  M ⊙ yr −1 . We also discuss the low oxygen abundance of the host galaxy derived from the MUSE data, having an average of 12 + log(O/H) = 8.27 +0.16 −0.20 using the O 3 N 2 diagnostic with strong line methods. We compared it with the supernova spectra, which is also consistent with a sub-Solar metallicity progenitor. Following recent observations of extraplanar H II regions in nearby edge-on galaxies, we derived the metallicity offset from the disk, being positive, but consistent with zero at 2 σ , suggesting enrichment from disk outflows. We finally discuss the possible scenarios for the unusual environment for ASASSN-14jb and conclude that either the in-situ star formation or runaway scenario would imply a low-mass progenitor, agreeing with our estimate from the supernova nebular spectrum. Regardless of the true origin of ASASSN-14jb, we show that the detailed study of the environment roughly agree with the stronger constraints from the observation of the transient. 

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4. N 3 -Ligated nickel( ii ) diketonate complexes: synthesis, characterization and evaluation of O 2 reactivity

   https://doi.org/10.1039/d0dt01338b  

   Elsberg, Josiah G. ; Peterson, Austin ; Fuller, Amy L. ; Berreau, Lisa M. ( January 2020 , Dalton Transactions)

   Interest in O 2 -dependent aliphatic carbon–carbon (C–C) bond cleavage reactions of first row divalent metal diketonate complexes stems from the desire to further understand the reaction pathways of enzymes such as DKE1 and to extract information to develop applications in organic synthesis. A recent report of O 2 -dependent aliphatic C–C bond cleavage at ambient temperature in Ni( ii ) diketonate complexes supported by a tridentate nitrogen donor ligand [(MBBP)Ni(PhC(O)CHC(O)Ph)]Cl ( 7-Cl ; MBBP = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine) in the presence of NEt 3 spurred our interest in further examining the chemistry of such complexes. A series of new TERPY-ligated Ni( ii ) diketonate complexes of the general formula [(TERPY)Ni(R 2 -1,3-diketonate)]ClO 4 ( 1 : R = CH 3 ; 2 : R = C(CH 3 ) 3 ; 3 : R = Ph) was prepared under air and characterized using single crystal X-ray crystallography, elemental analysis, 1 H NMR, ESI-MS, FTIR, and UV-vis. Analysis of the reaction mixtures in which these complexes were generated using 1 H NMR and ESI-MS revealed the presence of both the desired diketonate complex and the bis-TERPY derivative [(TERPY) 2 Ni](ClO 4 ) 2 ( 4 ). Through selective crystallization 1–3 were isolated in analytically pure form. Analysis of reaction mixtures leading to the formation of the MBBP analogs [(MBBP)Ni(R 2 -1,3-diketonate)]X (X = ClO 4 : 5 : R = CH 3 ; 6 : R = C(CH 3 ) 3 ; 7-ClO4 : R = Ph; X = Cl: 7-Cl : R = Ph) using 1 H NMR and ESI-MS revealed the presence of [(MBBP) 2 Ni](ClO 4 ) 2 ( 8 ). Analysis of aerobic acetonitrile solutions of analytically pure 1–3 , 5 and 6 containing NEt 3 and in some cases H 2 O using 1 H NMR and UV-vis revealed evidence for the formation of additional bis-ligand complexes ( 4 and 8 ) but suggested no oxidative diketonate cleavage reactivity. Analysis of the organic products generated from 3 , 7-ClO4 and 7-Cl revealed unaltered dibenzoylmethane. Our results therefore indicate that N 3 -ligated Ni( ii ) complexes of unsubstituted diketonate ligands do not exhibit O 2 -dependent aliphatic C–C bond clevage at room temperature, including in the presence of NEt 3 and/or H 2 O. 

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5. Chalcogen-atom abstraction reactions of a Di-iron imidophosphorane complex

   https://doi.org/10.1039/d1cc02195h  

   Aguirre Quintana, Luis M. ; Yang, Yan ; Ramanathan, Arun ; Jiang, Ningxin ; Bacsa, John ; Maron, Laurent ; La Pierre, Henry S. ( July 2021 , Chemical Communications)

   null (Ed.)

   Reaction of the complexes [Fe 2 (μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] ( 1-Fe ) and [Co 2 (μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] ( 1-Co ), where [NP(pip) 3 ] 1− is tris(piperidinyl)imidophosphorane, with nitrous oxide, S 8 , or Se 0 results in divergent reactivity. With nitrous oxide, 1-Fe forms [Fe 2 (μ 2 -O)(μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] ( 2-Fe ), with a very short Fe 3+ –Fe 3+ distance. Reactions of 1-Fe with S 8 or Se 0 result in the bridging, side-on coordination (μ-κ 1 :κ 1 -E 2 2− ) of the heavy chalcogens in complexes [Fe 2 (μ-κ 1 :κ 1 -E 2 )(μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] (E = S, 3-Fe , or Se, 4-Fe ). In all cases, the complex 1-Co is inert. 

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