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1. The importance of the counter-cation in reductive rare-earth metal chemistry: 18-crown-6 instead of 2,2,2-cryptand allows isolation of [Y ^II (NR ₂ ) ₃ ] ¹⁻ and ynediolate and enediolate complexes from CO reactions

   https://doi.org/10.1039/C9SC05794C  

   Ryan, Austin J. ; Ziller, Joseph W. ; Evans, William J. ( February 2020 , Chemical Science)

   The use of 18-crown-6 (18-c-6) in place of 2.2.2-cryptand (crypt) in rare earth amide reduction reactions involving potassium has proven to be crucial in the synthesis of Ln( ii ) complexes and isolation of their CO reduction products. The faster speed of crystallization with 18-c-6 appears to be important. Previous studies have shown that reduction of the trivalent amide complexes Ln(NR 2 ) 3 (R = SiMe 3 ) with potassium in the presence of 2.2.2-cryptand (crypt) forms the divalent [K(crypt)][Ln II (NR 2 ) 3 ] complexes for Ln = Gd, Tb, Dy, and Tm. However, for Ho and Er, the [Ln(NR 2 ) 3 ] 1− anions were only isolable with [Rb(crypt)] 1+ counter-cations and isolation of the [Y II (NR 2 ) 3 ] 1− anion was not possible under any of these conditions. We now report that by changing the potassium chelator from crypt to 18-crown-6 (18-c-6), the [Ln(NR 2 ) 3 ] 1− anions can be isolated not only for Ln = Gd, Tb, Dy, and Tm, but also for Ho, Er, and Y. Specifically, these anions are isolated as salts of a 1 : 2 potassium : crown sandwich cation, [K(18-c-6) 2 ] 1+ , i.e. [K(18-c-6) 2more »][Ln(NR 2 ) 3 ]. The [K(18-c-6) 2 ] 1+ counter-cation was superior not only in the synthesis, but it also allowed the isolation of crystallographically-characterizable products from reactions of CO with the [Ln(NR 2 ) 3 ] 1− anions that were not obtainable from the [K(crypt)] 1+ analogs. Reaction of CO with [K(18-c-6) 2 ][Ln(NR 2 ) 3 ], generated in situ , yielded crystals of the ynediolate products, {[(R 2 N) 3 Ln] 2 (μ-OCCO)} 2− , which crystallized with counter-cations possessing 2 : 3 potassium : crown ratios, i.e. {[K 2 (18-c-6) 3 ]} 2+ , for Gd, Dy, Ho. In contrast, reaction of CO with a solution of isolated [K(18-c-6) 2 ][Gd(NR 2 ) 3 ], produced crystals of an enediolate complex isolated with a counter-cation with a 2 : 2 potassium : crown ratio namely [K(18-c-6)] 2 2+ in the complex [K(18-c-6)] 2 {[(R 2 N) 2 Gd 2 (μ-OCHCHO) 2 ]}.« less
2. Evidence for AGN-regulated Cooling in Clusters at z ∼ 1.4: A Multiwavelength View of SPT-CL J0607-4448

   https://doi.org/10.3847/1538-4357/acae9e  

   Masterson, Megan ; McDonald, Michael ; Ansarinejad, Behzad ; Bayliss, Matthew ; Benson, Bradford A. ; Bleem, Lindsey E. ; Calzadilla, Michael S. ; Edge, Alastair C. ; Floyd, Benjamin ; Kim, Keunho J. ; et al ( February 2023 , The Astrophysical Journal)

   We present a multiwavelength analysis of the galaxy cluster SPT-CL J0607-4448 (SPT0607), which is one of the most distant clusters discovered by the South Pole Telescope atz= 1.4010 ± 0.0028. The high-redshift cluster shows clear signs of being relaxed with well-regulated feedback from the active galactic nucleus (AGN) in the brightest cluster galaxy (BCG). Using Chandra X-ray data, we construct thermodynamic profiles and determine the properties of the intracluster medium. The cool-core nature of the cluster is supported by a centrally peaked density profile and low central entropy ($K_0={18}_{-9}^{+11}$keV cm²), which we estimate assuming an isothermal temperature profile due to the limited spectral information given the distance to the cluster. Using the density profile and gas cooling time inferred from the X-ray data, we find a mass-cooling rate${\dot{M}}_{\mathrm{cool}}={100}_{-60}^{+90}{M}_{\odot }$yr⁻¹. From optical spectroscopy and photometry around the [Oii] emission line, we estimate that the BCG star formation rate is${\mathrm{SFR}}_{[\mathrm{O}\mathrm{II}]}={1.7}_{-0.6}^{+1.0}{M}_{\odot }$yr⁻¹, roughly two orders of magnitude lower than the predicted mass-cooling rate. In addition, using ATCA radio data at 2.1 GHz, we measure a radio jet power$P_{\mathrm{cav}}={3.2}_{-1.3}^{+2.1}\times {10}^{44}$erg s⁻¹, which is consistent withmore »the X-ray cooling luminosity ($L_{\mathrm{cool}}={1.9}_{-0.5}^{+0.2}\times {10}^{44}$erg s⁻¹withinr_cool= 43 kpc). These findings suggest that SPT0607 is a relaxed, cool-core cluster with AGN-regulated cooling at an epoch shortly after cluster formation, implying that the balance between cooling and feedback can be reached quickly. We discuss the implications for these findings on the evolution of AGN feedback in galaxy clusters.

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3. Reductive cleavage of N , N ′-di- tert -butylcarbodiimide generates tert -butylcyanamide ligands, (Me ₃ CNCN) ⁻ , that bind potassium both end-on and side-on in the same single crystal

   https://doi.org/10.1107/S205698902000732X  

   Chung, Amanda B. ; Ziller, Joseph W. ; Evans, William J. ( July 2020 , Acta Crystallographica Section E Crystallographic Communications)

   N , N ′-Di- tert -butylcarbodiimide, Me 3 CN=C=NCMe 3 , undergoes reductive cleavage in the presence of the Gd II complex, [K(18-crown-6) 2 ][Gd II (N R 2 ) 3 ] ( R = SiMe 3 ), to form a new type of ligand, the tert -butylcyanamide anion, (Me 3 CNCN) − . This new ligand can bind metals with one or two donor atoms as demonstrated by the isolation of a single crystal containing potassium salts of both end-on and side-on bound tert -butylcyanamide anions, (Me 3 CNCN) − . The crystal contains [K(18-crown-6)(H 2 O)][NCNCMe 3 - kN ], in which one ( t BuNCN) − anion is coordinated end-on to potassium ligated by 18-crown-6 and water, as well as [K(18-crown-6)][η 2 -NCNCMe 3 ], in which an 18-crown-6 potassium is coordinated side-on to the terminal N—C linkage. This single crystal also contains one equivalent of 1,3-di- tert -butyl urea, (C 9 H 20 N 2 O), which is involved in hydrogen bonding that may stabilize the whole assembly, namely, aqua( tert -butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)–( tert -butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)– N , N ′-di- tert -butylcarbodiimide (1/1/1) [K(C 5 H 9 N 2 )(C 12 H 24 O 6 )]·[K(C 5 Hmore »9 N 2 )(C 12 H 24 O 6 )(H 2 O)]·C 9 H 20 N 2 .« less
4. ALMA Reveals Extended Cool Gas and Hot Ionized Outflows in a Typical Star-forming Galaxy at Z = 7.13

   https://doi.org/10.3847/1538-4357/ac795b  

   Akins, Hollis B. ; Fujimoto, Seiji ; Finlator, Kristian ; Watson, Darach ; Knudsen, Kirsten K. ; Richard, Johan ; C. Bakx, Tom J. L. ; Hashimoto, Takuya ; Inoue, Akio K. ; Matsuo, Hiroshi ; et al ( July 2022 , The Astrophysical Journal)

   We present spatially resolved morphological properties of [CII] 158μm, [OIII] 88μm, dust, and rest-frame ultraviolet (UV) continuum emission for A1689-zD1, a strongly lensed, sub-L* galaxy atz= 7.13, by utilizing deep Atacama Large Millimeter/submillimeter Array (ALMA) and Hubble Space Telescope (HST) observations. While the [OIII] line and UV continuum are compact, the [CII] line is extended up to a radius ofr∼ 12 kpc. Using multi-band rest-frame far-infrared continuum data ranging from 52 to 400μm, we find an average dust temperature and emissivity index of$T_{\mathrm{dust}}={41}_{-14}^{+17}$K and$\beta ={1.7}_{-0.7}^{+1.1}$, respectively, across the galaxy. We find slight differences in the dust continuum profiles at different wavelengths, which may indicate that the dust temperature decreases with distance. We map the star formation rate (SFR) via IR and UV luminosities and determine a total SFR of 37 ± 1M_⊙yr⁻¹with an obscured fraction of 87%. While the [OIII] line is a good tracer of the SFR, the [CII] line shows deviation from the localL_[CII]-SFR relations in the outskirts of the galaxy. Finally, we observe a clear difference in the line profile between [CII] and [OIII], with significant residuals (∼5σ) in the [OIII] line spectrum after subtracting a single Gaussian model. This suggestsmore »a possible origin of the extended [CII] structure from the cooling of hot ionized outflows. The extended [CII] and high-velocity [OIII] emission may both contribute in part to the highL_[OIII]/L_[CII]ratios recently reported inz> 6 galaxies.

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5. Molecular Gas Excitation of the Massive Dusty Starburst CRLE and the Main-sequence Galaxy HZ10 at z = 5.7 in the COSMOS Field

   https://doi.org/10.3847/1538-4357/ac403a  

   Vieira, Daniel ; Riechers, Dominik A. ; Pavesi, Riccardo ; Faisst, Andreas L. ; Schinnerer, Eva ; Scoville, Nicholas Z. ; Stacey, Gordon J. ( February 2022 , The Astrophysical Journal)

   We report CO(5 → 4) and CO(6 → 5) line observations in the dusty starbursting galaxy CRLE (z= 5.667) and the main-sequence (MS) galaxy HZ10 (z= 5.654) with the Northern Extended Millimeter Array. CRLE is the most luminousz> 5 starburst in the COSMOS field and HZ10 is the most gas-rich “normal” galaxy currently known atz> 5. We find line luminosities for CO(5 → 4) and CO(6 → 5) of (4.9 ± 0.5) and (3.8 ± 0.4) × 10¹⁰K km s⁻¹pc²for CRLE and upper limits of < 0.76 and < 0.60 × 10¹⁰K km s⁻¹pc²for HZ10, respectively. The CO excitation of CRLE appears comparable to otherz> 5 dusty star-forming galaxies. For HZ10, these line luminosity limits provide the first significant constraints of this kind for an MS galaxy atz> 5. We find the upper limit of$L_{5\to 4}^{\prime }/L_{2\to 1}^{\prime }$in HZ10 could be similar to the average value for MS galaxies aroundz≈ 1.5, suggesting that MS galaxies with comparable gas excitation may already have existed one billion years after the Big Bang. For CRLE we determine the most likely values for the H₂density, kinetic temperature, and dust temperature based on excitation modeling of the CO line ladder. Wemore »also derive a total gas mass of (7.1 ± 1.3) × 10¹⁰M_⊙. Our findings provide some of the currently most detailed constraints on the gas excitation that sets the conditions for star formation in a galaxy protocluster environment atz> 5.

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