The Isocyanide–Cyanide Rearrangement; Mechanism and Preparative Applications
✍ Scribed by Prof. Dr. Christoph Rüchardt; Dr. Michael Meier; Dr. Klaus Haaf; Dr. Joachim Pakusch; Dipl.-Chem. Erwin K. A. Wolber; Dipl.-Chem. Barbara Müller
- Book ID
- 102726701
- Publisher
- John Wiley and Sons
- Year
- 1991
- Tongue
- English
- Weight
- 848 KB
- Volume
- 30
- Category
- Article
- ISSN
- 0044-8249
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Ab initio (STO-3G) geometry-optimized calctdations have been performed on methyl and trifluoromethyl cyanide and isocyanide, and energies of isomerization of 24.1 and 11.5 kcal/mole, respectively have been calculated. Activation barriers of 87.8 and 80.0 kwl/mole are predicted for the isomerization
Electron correlation corrections have a considerable influence on the relative stabilities of lithium isocyanide (l), lithium cyanide (2), and the bridged form, 3. While Hartree-Fock theory finds 1 to be most stable and 3 not to be a minimum, MP2/6-31G\* optimization indicates 3 to be the global min