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1. Geometrical variations of two manganese(II) complexes with closely related quinoline-based tripodal ligands

   https://doi.org/10.1107/S2056989021009786  

   Frey, Steven T. ; Ballot, Jasper G. ; Hands, Allison ; Cirka, Haley A. ; Rinaolo, Katheryn C. ; Phalkun, Nich N. ; Kaur, Manpreet ; Jasinski, Jerry P. ( October 2021 , Acta Crystallographica Section E Crystallographic Communications)

   Structural analyses of the compounds di-μ-acetato-κ 4 O : O ′-bis{[2-methoxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ]manganese(II)} bis(tetraphenylborate) dichloromethane 1.45-solvate, [Mn 2 (C 23 O 2 ) 2 (C 23 H 23 N 3 O) 2 ](C 24 H 20 B)·1.45CH 2 Cl 2 or [Mn(DQMEA)(μ-OAc) 2 Mn(DQMEA)](BPh 4 ) 2 ·1.45CH 2 Cl 2 or [1] (BPh 4 ) 2 ·1.45CH 2 Cl 2 , and (acetato-κ O )[2-hydroxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ](methanol-κ O )manganese(II) tetraphenylborate methanol monosolvate, [Mn(CH 3 COO)(C 22 H 21 N 3 O)(CH 3 OH)](C 24 H 20 B)·CH 3 OH or [Mn(DQEA)(OAc)(CH 3 OH)]BPh 4 ·CH 3 OH or [2] BPh 4 ·CH 3 OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to Mn II ions. In the asymmetric unit, compound [1] (BPh 4 ) 2 ·(CH 2 Cl 2 ) 1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitrogen, the nitrogen atom of each quinoline group, and the methoxy-oxygen of the tetradentate DQMEA ligand, and two bridging-acetatemore »oxygen atoms. The symmetric Mn II centers have a distorted, octahedral geometry in which the quinoline nitrogen atoms are trans to each other resulting in co-planarity of the quinoline rings. For each Mn II center, a coordinated acetate oxygen participates in C—H...O hydrogen-bonding interactions with the two quinolyl moieties, further stabilizing the trans structure. Within the crystal, weak π – π stacking interactions and intermolecular cation–anion interactions stabilize the crystal packing. In the asymmetric unit, compound [2] BPh 4 ·CH 3 OH crystallizes as a monomer in which the manganese(II) ion is coordinated to the central nitrogen, the nitrogen atom of each quinoline group, and the alcohol oxygen of the tetradentate DQEA ligand, an oxygen atom of OAc, and the oxygen atom of a methanol ligand. The geometry of the Mn II center in [2] BPh 4 ·CH 3 OH is also a distorted octahedron, but the quinoline nitrogen atoms are cis to each other in this structure. Hydrogen bonding between the acetate oxygen atoms and hydroxyl (O—H...O) and quinolyl (C—H...O and N—H...O) moieties of the DQEA ligand stabilize the complex in this cis configuration. Within the crystal, dimerization of complexes occurs by the formation of a pair of intermolecular O3—H3...O2 hydrogen bonds between the coordinated hydroxyl oxygen of the DQEA ligand of one complex and an acetate oxygen of another. Additional hydrogen-bonding and intermolecular cation–anion interactions contribute to the crystal packing.« less
2. 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, explosionmore »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.« less
3. Structural diversity in copper(I) iodide complexes with 6-thioxopiperidin-2-one, piperidine-2,6-dithione and isoindoline-1,3-dithione ligands

   https://doi.org/10.1107/S2056989020009676  

   Wheaton, Amelia M. ; Guzei, Ilia A. ; Berry, John F. ( August 2020 , Acta Crystallographica Section E Crystallographic Communications)

   Copper(I) iodide complexes are well known for displaying a diverse array of structural features even when only small changes in ligand design are made. This structural diversity is well displayed by five copper(I) iodide compounds reported here with closely related piperidine-2,6-dithione (SNS), isoindoline-1,3-dithione (SNS6), and 6-thioxopiperidin-2-one (SNO) ligands: di-μ-iodido-bis[(acetonitrile-κ N )(6-sulfanylidenepiperidin-2-one-κ S )copper(I)], [Cu 2 I 2 (CH 3 CN) 2 (C 5 H 7 NOS) 2 ] ( I ), bis(acetonitrile-κ N )tetra-μ 3 -iodido-bis(6-sulfanylidenepiperidin-2-one-κ S )- tetrahedro -tetracopper(I), [Cu 4 I 4 (CH 3 CN) 4 (C 5 H 7 NOS) 4 ] ( II ), catena -poly[[(μ-6-sulfanylidenepiperidin-2-one-κ 2 O : S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NOS)] n ( III ), poly[[(piperidine-2,6-dithione-κ S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NS 2 )] n ( IV ), and poly[[(μ-isoindoline-1,3-dithione-κ 2 S : S )copper(I)]-μ 3 -iodido], [CuI(C 8 H 5 NS 2 )] n ( V ). Compounds I and II crystallize as discrete dimeric and tetrameric complexes, whereas III , IV , and V crystallize as polymeric two-dimensional sheets. To the best of our knowledge, compound III is the first instance of an extended hexagonal [Cu 3 I 3 ] structure that is notmore »supported by bridging ligands. Structures I , II , and IV display weak to moderately strong Cu...Cu cuprophilic interactions [Cu...Cu internuclear distances range between 2.5803 (10) and 2.8485 (14) Å]. All structures except III display weak hydrogen-bonding interactions between the N—H of the ligand and the μ 2 and μ 3 -I − atoms. Structure III contains classical N–H...O interactions between the SNO ligands that connect the molecules in a three-dimensional framework. Complex V features π–π stacking interactions between the aryl rings of the SNS6 ligands within the same polymeric sheet. In structure IV , there were three partially occupied solvent molecules of dichloromethane and one partially occupied molecule of acetonitrile present in the asymmetric unit. The SQUEEZE routine [Spek (2015). Acta Cryst . C 71 , 9–18] was used to correct the diffraction data for diffuse scattering effects and to identify the solvent molecules. The given chemical formula and other crystal data do not take into account the solvent molecules.« less
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 inmore »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.« less
5. En route to diplatinum polyynediyl complexes trans,trans-(Ar)(R3P)2Pt(C≡C)nPt(PR3)2(Ar): Untold tales, including end-group strategies

   https://doi.org/10.1351/pac200880030459  

   Stahl, Jürgen ; Bohling, James C. ; Peters, Thomas B. ; de Quadras, Laura ; Gladysz, John A. ( January 2008 , Pure and Applied Chemistry)

   Reactions of {(C 6 F 5 )Pt[S(CH 2 CH 2 -) 2 ](μ-Cl)} 2 and R 3 P yield the bis(phosphine) species trans -(C 6 F 5 )(R 3 P) 2 PtCl [R = Et ( Pt'Cl ), Ph, ( p -CF 3 C 6 H 4 ) 3 P; 88-81 %]. Additions of Pt'Cl and H(C≡C) n H ( n = 1, 2; HNEt 2 , 20 mol % CuI) give Pt'C 2 H (37 %, plus Pt'I , 16 %) and Pt'C 4 H (88 %). Homocoupling of Pt'C 4 H under Hay conditions (O 2 , CuCl, TMEDA, acetone) gives Pt'C 8 Pt' (85 %), but Pt'C 2 H affords only traces of Pt'C 4 Pt' . However, condensation of Pt'C 4 H and Pt'Cl (HNEt 2 , 20 mol % CuI) yields Pt'C 4 Pt' (97 %). Hay heterocouplings of Pt'C 4 H or trans -( p -tol)(Ph 3 P) 2 Pt(C≡C) 2 H ( Pt*C 4 H ) and excess HC≡CSiEt 3 give Pt'C 6 SiEt 3 (76 %) or Pt*C 6 SiEt 3 (89 %). The latter and wet n -Bu 4 N + F - react to yield labile Pt*C 6 H (60more »%). Hay homocouplings of Pt*C 4 H and Pt*C 6 H give Pt*C 8 Pt* (64 %) and Pt*C 12 Pt* (64 %). Reaction of trans -(C 6 F 5 )( p -tol 3 P) 2 PtCl ( PtCl ) and HC≡CH (HNEt 2 , 20 mol % CuI) yields only traces of PtC 2 H . However, an analogous reaction with HC≡CSiMe 3 gives PtC 2 SiMe 3 (75 %), which upon treatment with silica yields PtC 2 H (77 %). An analogous coupling of trans -(C 6 F 5 )(Ph 3 P) 2 PtCl with H(C≡C) 2 H gives trans -(C 6 F 5 )(Ph 3 P) 2 Pt(C≡C) 2 H (34 %). Advantages and disadvantages of the various trans -(Ar)(R 3 P) 2 Pt end-groups are analyzed.« less