Substituent effects on singlet-triplet gaps and mechanisms of 1,2-rearrangements of 1,3-oxazol-2-ylidenes to 1,3-oxazoles

The Journal of Physical Chemistry. a
Fillmore FreemanJustin D Willey

Abstract

Electronic structures, partial atomic charges, singlet-triplet gaps (Delta E ST), substituent effects, and mechanisms of 1,2-rearrangements of 1,3-oxazol-2-ylidene ( 5) and 4,5-dimethyl- ( 6), 4,5-difluoro- ( 7), 4,5-dichloro- ( 8), 4,5-dibromo- ( 9), and 3-methyl-1,3-oxazol-2-ylidene ( 10) to the corresponding 1,3-oxazoles have been studied using complete-basis-set methods (CBS-QB3, CBS-Q, CBS-4M), second-order Møller-Plesset perturbation method (MP2), hybrid density functionals (B3LYP, B3PW91), coupled-cluster theory with single and double excitations (CCSD) and CCSD plus perturbative triple excitations [CCSD(T)], and the quadratic configuration interaction method including single and double excitations (QCISD) and QCISD plus perturbative triple excitations [QCISD(T)]. The 6-311G(d,p), 6-31+G(d,p), 6-311+G(d,p), and correlation-consistent polarized valence double-xi (cc-pVDZ) basis sets were employed. The carbenes have singlet ground states, and the CBS-QB3 and CBS-Q methods predict Delta E ST values for 5- 8 and 10 of 79.9, 79.8, 74.7, 77.0, and 82.0 kcal/mol, respectively. CCSD(T), QCISD(T), B3LYP, and B3PW91 predict smaller Delta E ST values than CBS-QB3 and CBS-Q, with the hybrid density functionals predicting the smalles...Continue Reading

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Citations

Jun 18, 2009·Chemical Communications : Chem Comm·Javier Ruiz, Bernabé F Perandones
Mar 9, 2017·Environmental Technology·Sowmya Vilvanathan, S Shanthakumar
May 5, 2017·Environmental Technology·Mohammad Amin NazariMuhammed A Bhuiyan
Mar 31, 2018·Environmental Technology·Ahed ZyoudHikmat S Hilal
Nov 5, 2014·Journal of Computational Chemistry·Andrey A KirilchukAlexander B Rozhenko
Jan 30, 2010·The Journal of Physical Chemistry. a·Barbara Michela GiulianoRui Fausto
Jan 31, 2019·Organic Letters·Svetlana V KlementyevaAndrey I Poddel'sky
Dec 14, 2021·The Journal of Organic Chemistry·Anatoliy MarchenkoAleksandr Kostyuk

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