[reaction: see text] Both DFT and CCSD and CCSD(T) computational methods indicate that 1-fluorocyclopropene can undergo an unprecedented "electrocyclic" automerization process involving a full 180 degrees rotation of its methylene group, without the formation of an intermediate carbene or diradical.
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http://dx.doi.org/10.1021/ol0169574 | DOI Listing |
Phys Chem Chem Phys
August 2021
School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S C Mullick Road, Kolkata 700032, India.
Cyclobutadiene (CBD) is the paradigmatic antiaromatic molecule but is known to form highly stable aromatic complexes, e.g. CBD-Fe(CO)3.
View Article and Find Full Text PDFJ Org Chem
December 2017
Department of Chemistry and Materials Science Program, University of New Hampshire, Durham, New Hampshire 03824, United States.
In 1 M triflic acid/dichloroethane, anthracene is protonated at C9, and the resulting 9-anthracenium ion is easily observed by NMR at ambient temperature. When heated as a dilute solution in triflic acid/dichloroethane, anthracene undergoes conversion to phenanthrene as the major volatile product. Minor dihydro and tetrahydro products are also observed.
View Article and Find Full Text PDFJ Chem Theory Comput
November 2014
Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, L8S 4M1 Ontario, Canada.
We introduce new nonvariational orbital optimization schemes for the antisymmetric product of one-reference orbital geminal (AP1roG) wave function (also known as pair-coupled cluster doubles) that are extensions to our recently proposed projected seniority-two (PS2-AP1roG) orbital optimization method [ J. Chem. Phys.
View Article and Find Full Text PDFJ Chem Theory Comput
July 2015
Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel.
The π bond shifting (automerization) by carbon tunneling of cyclopropenyl anions was computationally analyzed by the small curvature tunneling methodology. Similar to other antiaromatic cases, the process is hindered by substituents departing from planarity, since these groups must be realigned along with the π bond shifting. With hydrogens as substituents the tunneling is extremely fast, in a case of both heavy and light atom tunneling.
View Article and Find Full Text PDFJ Org Chem
January 2011
Department of Chemistry, University of San Francisco, 2130 Fulton Street, San Francisco, California 94117, United States.
Density functional and coupled cluster calculations on neutral monodehydro[12]annulenes (C(12)H(10)) reveal a global minimum that should be kinetically stable. At the CCSD(T)/cc-pVDZ//BHLYP/6-31G* level, the unsymmetrical CTCTC conformer 1a lies at least 3 kcal/mol below all other isomers studied. The two isomers closest in energy to 1a are Möbius structure 5a (CCTCC) and all-cis 6a.
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