A Stable Aluminum Tris(dithiolene) Triradical
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Lahm, Mitchell E.
Publications and source records attributed to Lahm, Mitchell E..
Unusual nucleophilic reactivity of a dithiolene-based N-heterocyclic silane
Dithiolene-based N-heterocyclic silane demonstrates unusual dual nucleophilic reactivity toward boron halides.
Chemistry↗
Correction: Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance
Correction for ‘Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance’ by Pascal Vermeeren et al. , Phys. Chem. Chem. Phys. , 2022, 24 , 18028–18042, https://doi.org/10.1039/D2CP02234F.
Vermeeren, Pascal↗
Structures and Energetics of E 2 H 3 + (E = As, Sb, and Bi) Cations
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
From Carbene-Dithiolene Zwitterion Mediated B–H Bond Activation to BH 3 ·SMe 2 -Assisted Boron–Boron Bond Formation
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Germanium(II) Dithiolene Complexes
The 1 : 2 reaction of the imidazole-based dithiolate (2) with GeCl 2 • dioxane in THF/TMEDA gives 3, a TMEDA-complexed dithiolene-based germylene. Compound 3 is converted to monothiolate-complexed (5) and N-heterocyclic carbene-complexed (7) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis-dithiolene-based germylene (8), involving a 3c–4e S-Ge-S bond, has also been synthesized through controlled hydrolysis of 7. The bonding nature of 3, 5, and 8 was investigated by both experimental and theoretical methods.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The multichannel i -propyl + O2 reaction system: A model of secondary alkyl radical oxidation
The i-propyl + O2 reaction mechanism has been investigated by definitive quantum chemical methods to establish this system as a benchmark for the combustion of secondary alkyl radicals. Focal point analyses extrapolating to the ab initio limit were performed based on explicit computations with electron correlation treatments through coupled cluster single, double, triple, and quadruple excitations and basis sets up to cc-pV5Z. The rigorous coupled cluster single, double, and triple excitations/cc-pVTZ level of theory was used to fully optimize all reaction species and transition states, thus, removing some substantial flaws in reference geometries existing in the literature. The vital i-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1) were found 34.8 and 4.4 kcal mol−1 below the reactants, respectively. Two β-hydrogen transfer transition states (TS2, TS2′) lie above the reactants by (1.4, 2.5) kcal mol−1 and display large Born–Oppenheimer diagonal corrections indicative of nearby surface crossings. An α-hydrogen transfer transition state (TS5) is discovered 5.7 kcal mol−1 above the reactants that bifurcates into equivalent α-peroxy radical hanging wells (MIN3) prior to a highly exothermic dissociation into acetone + OH. The reverse TS5 → MIN1 intrinsic reaction path also displays fascinating features, including another bifurcation and a conical intersection of potential energy surfaces. An exhaustive conformational search of two hydroperoxypropyl (QOOH) intermediates (MIN2 and MIN3) of the i-propyl + O2 system located nine rotamers within 0.9 kcal mol−1 of the corresponding lowest-energy minima.
Chemistry↗