Ab initio/GIAO-CCSD(T) study of propenoyl (H2C=CH-CO+) and isopentenoyl ((CH3)2C=CH-CO+) cations and their superelectrophilic protonated dications

Golam Rasul; G K Surya Prakash; George A Olah

doi:10.1021/jp058236i

Ab initio/GIAO-CCSD(T) study of propenoyl (H2C=CH-CO+) and isopentenoyl ((CH3)2C=CH-CO+) cations and their superelectrophilic protonated dications

J Phys Chem A. 2006 Jan 26;110(3):1041-5. doi: 10.1021/jp058236i.

Authors

Golam Rasul¹, G K Surya Prakash, George A Olah

Affiliation

¹ Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661, USA. [email protected]

PMID: 16420005
DOI: 10.1021/jp058236i

Abstract

Structures of superelectrophilic protonated propenoyl (H2C=CH-COH2+) and isopentenoyl ((CH3)2C=CH-COH2+) dications and their parent cations were calculated using ab initio methods at the MP2/6-311+G and MP2/cc-pVTZ levels. Energies were calculated using Gaussian-2 (G2) theory. The alpha-carbon (Calpha) protonated 3 and 7 were found to be the global minima for protonated propenoyl and isopentenoyl dications, respectively. 13C NMR chemical shifts of the cations were also calculated using the GIAO-CCSD(T), GIAO-MP2 and GIAO-SCF methods. 13C NMR chemical shifts of the related tert-butyl cation ((CH3)3C+) and protonated tert-butyl dication ((CH3)2CCH4(2+)) were also computed at the same level to compare and explore the effect of the additional charge in dications.