Non‐empirical calculations of NMR indirect carbon–carbon coupling constants. Part 8—Monocycloalkanes

Abstract

Carbon-carbon and carbon-hydrogen spin-spin coupling constants were calculated in the series of the first six monocycloalkanes using SOPPA and SOPPA(CCSD) methods, and very good agreement with the available experimental data was achieved, with the latter method showing slightly better results in most cases, at least in those involving calculations of J(C,C). Benchmark calculations of all possible 21 coupling constants J(C,C), J(C,H) and J(H,H) in chair cyclohexane revealed the importance of using the appropriate level of theory and adequate quality of the basis sets. Many unknown couplings in this series were predicted with high confidence and several interesting structural trends (hybridization effects, multipath coupling transmission mechanisms, hyperconjugative interactions) were elucidated and are discussed based on the present calculations of spin-spin couplings.