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1. Unexpected alkyl isomerization at the silicon ligand of an unsaturated Rh complex: combined experiment and theory

   https://doi.org/10.1039/D3DT02087H  

   Abeynayake, Niroshani S; Le, Nghia; Sanchez-Lecuona, Gabriela; Donnadieu, Bruno; Webster, Charles Edwin; Montiel-Palma, Virginia (November 2023, Dalton Transactions)

   The formation of dimer [(μ-Cl)Rh-(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)(o-C6H4CH2SiiPrnPr))]2 (Rh-3) with an n-propyl group on one of the silicon atoms as a minor product was affected by the reaction of [RhCl(COD)]2 with proligand PhP(o-C6H4CH2SiHiPr2)2, L1. The major product of the reaction was monomeric 14-electron Rh(III) complex [ClRh(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2)] (Rh-1). Computations revealed that the monomer–dimer equilibrium is shifted toward the monomer with four isopropyl substituents on the two Si atoms of the ligand as in Rh-1; conversely, the dimer is favored with only one n-propyl as in Rh-3, and with less bulky alkyl substituents such as in [ClRh(κ3(P,Si,Si)PhP(o-C6H4CH2SiMe2)2]2 (Rh-2). Computations on the mechanism of formation of Rh-3 directly from [RhCl(COD)]2 are in agreement with the experimental findings and it is found to be less energetic than if stemming from Rh-1. Additionally, a Si–O–Si complex, [μ-Cl-Rh{κ3(P,Si,C)PPh(o-C6H4CH2SiiPrO SiiPr2CH-o-C6H4)}]2, Rh-4, is generated from the reaction of Rh-1 with adventitious water as a result of intramolecular C–H activation. 

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2. Nickel-mediated N–N bond formation and N ₂ O liberation via nitrogen oxyanion reduction

   https://doi.org/10.1039/D1SC02846D  

   Beagan, Daniel M.; Cabelof, Alyssa C.; Pink, Maren; Carta, Veronica; Gao, Xinfeng; Caulton, Kenneth G. (August 2021, Chemical Science)

   The syntheses of (DIM)Ni(NO 3 ) 2 and (DIM)Ni(NO 2 ) 2 , where DIM is a 1,4-diazadiene bidentate donor, are reported to enable testing of bis boryl reduced N-heterocycles for their ability to carry out stepwise deoxygenation of coordinated nitrate and nitrite, forming O(Bpin) 2 . Single deoxygenation of (DIM)Ni(NO 2 ) 2 yields the tetrahedral complex (DIM)Ni(NO)(ONO), with a linear nitrosyl and κ 1 -ONO. Further deoxygenation of (DIM)Ni(NO)(ONO) results in the formation of dimeric [(DIM)Ni(NO)] 2 , where the dimer is linked through a Ni–Ni bond. The lost reduced nitrogen byproduct is shown to be N 2 O, indicating N–N bond formation in the course of the reaction. Isotopic labelling studies establish that the N–N bond of N 2 O is formed in a bimetallic Ni 2 intermediate and that the two nitrogen atoms of (DIM)Ni(NO)(ONO) become symmetry equivalent prior to N–N bond formation. The [(DIM)Ni(NO)] 2 dimer is susceptible to oxidation by AgX (X = NO 3 − , NO 2 − , and OTf − ) as well as nitric oxide, the latter of which undergoes nitric oxide disproportionation to yield N 2 O and (DIM)Ni(NO)(ONO). We show that the first step in the deoxygenation of (DIM)Ni(NO)(ONO) to liberate N 2 O is outer sphere electron transfer, providing insight into the organic reductants employed for deoxygenation. Lastly, we show that at elevated temperatures, deoxygenation is accompanied by loss of DIM to form either pyrazine or bipyridine bridged polymers, with retention of a BpinO − bridging ligand. 

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3. Synthesis, electropolymerization and functionalization via click chemistry of N -alkynylated dithieno[3,2- b :2′,3′- d ]pyrrole

   https://doi.org/10.1039/d2ra03265a  

   Bandera, Yuriy; Jones, Haley W.; Grant, Benjamin; Mell, Sarah; Foulger, Stephen H. (October 2022, RSC Advances)

   A new N-alkynylated dithieno[3,2- b :2′,3′- d ]pyrrole (DTP) monomer was synthesized using a Buchwald–Hartwig amination of 3,3′-dibromo-2,2′-bithiophene with pent-4-yn-1-amine. The obtained monomer was investigated for the possibility of a pre-polymerization modification via Huisgen 1,3-dipolar cycloaddition (“click”) reaction with azide-containing organic compounds. The synthesized N-alkynylated DTP monomer is soluble in a number of organic solvents and reacts with organic azides via “click” reactions in mild conditions, achieving high yields. The N-alkynylated DTP monomer and its “click”-modified derivative can be electropolymerized to form polymeric films. Herein, the synthesis and characterization of a “click” modified DTP monomer, its pre-modified derivative, and their corresponding polymers are described. The developed method is a facile route to synthesize a new generation of various N-functionalized DTP homopolymers. 

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4. A plane defect in the 3d O(N) model

   https://doi.org/10.21468/SciPostPhys.15.3.090  

   Krishnan, Abijith; Metlitski, Max A (September 2023, SciPost Physics)

   It was recently found that the classical 3d O(N) model in the semi-infinite geometry can exhibit an “extraordinary-log” boundary universality class, where the spin-spin correlation function on the boundary falls off as < S(x) S(0)> ~ 1/ (log x)^q. This universality class exists for a range 2 ≤ N < Nc and Monte-Carlo simulations and conformal bootstrap indicate Nc > 3. In this work, we extend this result to the 3d O(N) model in an infinite geometry with a plane defect. We use renormalization group (RG) to show that in this case the extraordinary-log universality class is present for any finite N ≥ 2. We additionally show, in agreement with our RG analysis, that the line of defect fixed points which is present at infinite N is lifted to the ordinary, special (no defect) and extraordinary-log universality classes by 1/N corrections. We study the “central charge” a for the O(N) model in the boundary and interface geometries and provide a non-trivial detailed check of an a-theorem by Jensen and O’Bannon. Finally, we revisit the problem of the O(N) model in the semi-infinite geometry. We find evidence that at N = Nc the extraordinary and special fixed points annihilate and only the ordinary fixed point is left for N > Nc . 

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5. Unveiling the warm and dense ISM in z  > 6 quasar host galaxies via water vapor emission

   https://doi.org/10.1051/0004-6361/202243406  

   Pensabene, A.; van der Werf, P.; Decarli, R.; Bañados, E.; Meyer, R. A.; Riechers, D.; Venemans, B.; Walter, F.; Weiß, A.; Brusa, M.; et al (November 2022, Astronomy & Astrophysics)

   Water vapor (H₂O) is one of the brightest molecular emitters after carbon monoxide (CO) in galaxies with high infrared (IR) luminosity, allowing us to investigate the warm and dense phase of the interstellar medium (ISM) where star formation occurs. However, due to the complexity of its radiative spectrum, H₂O is not frequently exploited as an ISM tracer in distant galaxies. Therefore, H₂O studies of the warm and dense gas at high-zremain largely unexplored. In this work, we present observations conducted with the Northern Extended Millimeter Array (NOEMA) toward threez > 6 IR-bright quasarsJ2310+1855,J1148+5251, andJ0439+1634targeted in their multiple para- and ortho-H₂O transitions (3₁₂ − 3₀₃, 1₁₁ − 0₀₀, 2₂₀ − 2₁₁, and 4₂₂ − 4₁₃), as well as their far-IR (FIR) dust continuum. By combining our data with previous measurements from the literature, we estimated the dust masses and temperatures, continuum optical depths, IR luminosities, and star formation rates (SFR) from the FIR continuum. We modeled the H₂O lines using the MOLPOP-CEP radiative transfer code, finding that water vapor lines in our quasar host galaxies are primarily excited in the warm, dense (with a gas kinetic temperature and density ofT_kin = 50 K,n_H2 ∼ 10^4.5 − 10⁵ cm⁻³) molecular medium with a water vapor column density ofN_H2O ∼ 2 × 10¹⁷ − 3 × 10¹⁸ cm⁻³. High-JH₂O lines are mainly radiatively pumped by the intense optically-thin far-IR radiation field associated with a warm dust component at temperatures ofT_dust ∼ 80 − 190 K that account for < 5 − 10% of the total dust mass. In the case of J2310+1855, our analysis points to a relatively high value of the continuum optical depth at 100 μm (τ₁₀₀ ∼ 1). Our results are in agreement with expectations based on the H₂O spectral line energy distribution of local and high-zultra-luminous IR galaxies and active galactic nuclei (AGN). The analysis of the Boltzmann diagrams highlights the interplay between collisions and IR pumping in populating the high H₂O energy levels and it allows us to directly compare the excitation conditions in the targeted quasar host galaxies. In addition, the observations enable us to sample the high-luminosity part of the H₂O–total-IR (TIR) luminosity relations (L_H2O − L_TIR). Overall, our results point to supralinear trends that suggest H₂O–TIR relations are likely driven by IR pumping, rather than the mere co-spatiality between the FIR continuum- and line-emitting regions. The observedL_H2O/L_TIRratios in ourz > 6 quasars do not show any strong deviations with respect to those measured in star-forming galaxies and AGN at lower redshifts. This supports the notion that H₂O can be likely used to trace the star formation activity buried deep within the dense molecular clouds. 

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