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1. Binuclear Alkyne Manganese Carbonyls: Their Rearrangements to Allene, Allyl, and Vinylcarbene Derivatives by Hydrogen Migration from Methyl Substituents

   https://doi.org/10.1002/ejic.202100375  

   Hu, Yucheng ; Wang, Huijie ; Ji, Yupin ; Li, Huidong ; Fan, Qunchao ; King, R. Bruce ; Schaefer, III, Henry F. ( December 2021 , European Journal of Inorganic Chemistry)

   Binuclear alkyne manganese carbonyls of the type (RC≡CR')Mn₂(CO)_n(R and R'=methyl or dimethylamino;n=8, 7, 6) and their isomers related to the experimentally known (MeC₂NEt₂)Mn₂(CO)_n(n=8, 7) structures have been investigated by density functional theory. The alkyne ligand remains intact in the only low energy (Me₂N)₂C₂Mn₂(CO)₈isomer, which has a central Mn₂C₂tetrahedrane unit and is otherwise analogous to the well‐known (alkyne)Co₂(CO)₆derivatives except for one more CO group per metal atom. The low‐energy structures of the unsaturated (Me₂N)₂C₂Mn₂(CO)_n(n=7, 6) systems include isomers in which the nitrogen atom of one of the dimethylamino groups as well as the C≡C triple bond of the alkyne is coordinated to the central Mn₂unit. In other low‐energy (Me₂N)₂C₂Mn₂(CO)_n(n=7, 6) isomers the alkyne C≡C triple bond has broken completely to form two separate bridging dimethylaminocarbyne Me₂NC ligands analogous to the experimentally known iron carbonyl complex (Et₂NC)₂Fe₂(CO)₆. The (alkyne)Mn₂(CO)_n(n=8, 7, 6) systems of the alkynes MeC≡CMe and Me₂NC≡CMe with methyl substituents have significantly more complicated potential surfaces. In these systems the lowest energy isomers have bridging ligands derived from the alkyne in which one or two hydrogen atoms have migrated from a methyl group to one or both of the alkyne carbon atoms. These bridging ligands include allene, manganallyl, and vinylcarbenemore »ligands, the first two of which have been realized experimentally in research by Adams and coworkers. Theoretical studies suggest that the mechanism for the conversion of the simple alkyne octacarbonyl (MeC₂NMe₂)Mn₂(CO)₈to the dimethylaminomanganaallyl complex Mn₂(CO)₇[μ‐η⁴‐C₃H₃Me₂] involves decarbonylation to the heptacarbonyl and the hexacarbonyl complexes. Subsequent hydrogen migrations then occur through intermediates with C−H−Mn agostic interactions to give the final product. Eight transition states for this mechanistic sequence have been identified with activation energies of ∼20 kcal/mol for the first hydrogen migration and ∼14 kcal/mol for the second hydrogen migration.

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2. Computational predictions on Brønsted acidic ionic liquid-catalyzed carbon dioxide conversion to five-membered heterocyclic carbonyl derivatives

   https://doi.org/10.1039/d2cp05877d  

   Abdullayev, Yusif ; Karimova, Nazani ; Schenberg, Leonardo A. ; Ducati, Lucas C. ; Autschbach, Jochen ( March 2023 , Physical Chemistry Chemical Physics)

   Experimentally conducted reactions between CO 2 and various substrates ( i.e. , ethylenediamine (EDA), ethanolamine (ETA), ethylene glycol (EG), mercaptoethanol (ME), and ethylene dithiol (EDT)) are considered in a computational study. The reactions were previously conducted under harsh conditions utilizing toxic metal catalysts. We computationally utilize Brønsted acidic ionic liquid (IL) [Et 2 NH 2 ]HSO 4 as a catalyst aiming to investigate and propose ‘greener’ pathways for future experimental studies. Computations show that EDA is the best to fixate CO 2 among the tested substrates: the nucleophilic EDA attack on CO 2 is calculated to have a very small energy barrier to overcome (TS1EDA, Δ G ‡ = 1.4 kcal mol −1 ) and form I1EDA (carbamic acid adduct). The formed intermediate is converted to cyclic urea (PEDA, imidazolidin-2-one) via ring closure and dehydration of the concerted transition state (TS2EDA, Δ G ‡ = 32.8 kcal mol −1 ). Solvation model analysis demonstrates that nonpolar solvents (hexane, THF) are better for fixing CO 2 with EDA. Attaching electron-donating and -withdrawing groups to EDA does not reduce the energy barriers. Modifying the IL via changing the anion part (HSO 4 − ) central S atom with 6 A and 5more »A group elements (Se, P, and As) shows that a Se-based IL can be utilized for the same purpose. Molecular dynamics (MD) simulations reveal that the IL ion pairs can hold substrates and CO 2 molecules via noncovalent interactions to ease nucleophilic attack on CO 2 .« less
3. Sub-Doppler infrared spectroscopy of resonance-stabilized hydrocarbon intermediates: ν ₃ / ν ₄ CH stretch modes and CH ₂ internal rotor dynamics of benzyl radical

   https://doi.org/10.1039/c7cp05776h  

   Kortyna, A. ; Samin, A. J. ; Miller, T. A. ; Nesbitt, D. J. ( January 2017 , Physical Chemistry Chemical Physics)

   Highly reactive benzyl radicals are generated by electron dissociative attachment to benzyl chloride doped into a neon–hydrogen–helium discharge and immediately cooled to T rot = 15 K in a high density, supersonic slit expansion environment. The sub-Doppler spectra are fit to an asymmetric-top rotational Hamiltonian, thereby yielding spectroscopic constants for the ground ( v = 0) and first excited ( v = 1, ν 3 , ν 4 ) vibrational levels of the ground electronic state. The rotational constants obtained for the ground state are in good agreement with previous laser induced fluorescence measurements (LIF), with vibrational band origins ( ν 3 = 3073.2350 ± 0.0006 cm −1 , ν 4 = 3067.0576 ± 0.0006 cm −1 ) in agreement with anharmonically corrected density functional theory calculations. To assist in detection of benzyl radical in the interstellar medium, we have also significantly improved the precision of the ground state rotational constants through combined analysis of the ground state IR and LIF combination differences. Of dynamical interest, there is no evidence in the sub-Doppler spectra for tunneling splittings due to internal rotation of the CH 2 methylene subunit, which implies a significant rotational barrier consistent with partial double bond character inmore »the CC bond. This is further confirmed with high level ab initio calculations at the CCSD(T)-f12b/ccpVdZ-f12 level, which predict a zero-point energy corrected barrier to internal rotation of Δ E tun ≈ 11.45 kcal mol −1 or 4005 cm −1 . In summary, the high-resolution infrared spectra are in excellent agreement with simple physical organic chemistry pictures of a strongly resonance-stabilized benzyl radical with a nearly rigid planar structure due to electron delocalization around the aromatic ring.« less
4. High-resolution CH stretch spectroscopy of jet-cooled cyclopentyl radical: First insights into equilibrium structure, out-of-plane puckering, and IVR dynamics

   https://doi.org/10.1063/5.0096946  

   Kortyna, Andrew ; Reber, Melanie A. ; Nesbitt, David J. ( July 2022 , The Journal of Chemical Physics)

   First, high-resolution sub-Doppler infrared spectroscopic results for cyclopentyl radical (C 5 H 9 ) are reported on the α-CH stretch fundamental with suppression of spectral congestion achieved by adiabatic cooling to T rot ≈ 19(4) K in a slit jet expansion. Surprisingly, cyclopentyl radical exhibits a rotationally assignable infrared spectrum, despite 3N − 6 = 36 vibrational modes and an upper vibrational state density (ρ ≈ 40–90 #/cm −1 ) in the critical regime (ρ ≈ 100 #/cm −1 ) necessary for onset of intramolecular vibrational relaxation (IVR) dynamics. Such high-resolution data for cyclopentyl radical permit detailed fits to a rigid-rotor asymmetric top Hamiltonian, initial structural information for ground and vibrationally excited states, and opportunities for detailed comparison with theoretical predictions. Specifically, high level ab initio calculations at the coupled-cluster singles, doubles, and perturbative triples (CCSD(T))/ANO0, 1 level are used to calculate an out-of-plane bending potential, which reveals a C 2 symmetry double minimum 1D energy surface over a C 2v transition state. The inversion barrier [V barrier ≈ 3.7(1) kcal/mol] is much larger than the effective moment of inertia for out-of-plane bending, resulting in localization of the cyclopentyl wavefunction near its C 2 symmetry equilibrium geometry and tunneling splittingsmore »for the ground state too small (<1 MHz) to be resolved under sub-Doppler slit jet conditions. The persistence of fully resolved high-resolution infrared spectroscopy for such large cyclic polyatomic radicals at high vibrational state densities suggests a “deceleration” of IVR for a cycloalkane ring topology, much as low frequency torsion/methyl rotation degrees of freedom have demonstrated a corresponding “acceleration” of IVR processes in linear hydrocarbons.« less
5. Aromatic ouroboroi: heterocycles involving a σ-donor–acceptor bond and 4 n + 2 π-electrons

   https://doi.org/10.1039/c9cp05071j  

   Báez-Grez, Rodrigo ; Inostroza, Diego ; García, Victor ; Vásquez-Espinal, Alejandro ; Donald, Kelling J. ; Tiznado, William ( January 2020 , Physical Chemistry Chemical Physics)

   The aromaticity and dynamics of a set of recently proposed neutral 5- and 6-membered heterocycles that are closed by dative (donor–acceptor) or multi-center σ bonds, and have resonance forms with a Hückel number of π-electrons, are examined. The donors and acceptors in the rings include N, O, and F, and B, Be, and Mg, respectively. The planar geometry of the rings, coupled with evidence from different measures of aromaticity, namely the NICS zz , and NICS πzz components of the conventional nucleus independent chemical shifts (NICS), and ring current strengths (RCS), indicate non-trivial degrees of aromaticity in certain cases, including the cyclic C 3 B 2 OH 6 and C 3 BOH 5 isomers, both with three bonds to the O site in the ring. The former is lower in energy by at least 17.6 kcal mol −1 relative to linear alternatives obtained from molecular dynamics simulations in this work. Some of the other systems examined are best described as non-aromatic. Ring opening, closing, and isomerization are observed in molecular dynamics simulations for some of the systems studied. In a few cases, the ring indeed persists.