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Non‐empirical calculations of NMR indirect carbon–carbon coupling constants: 2. Strained polycarbocycles
Author(s) -
Krivdin Leonid B.
Publication year - 2003
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1135
Subject(s) - propellane , chemistry , propagator , coupling constant , computational chemistry , carbon 13 nmr , molecular physics , stereochemistry , quantum mechanics , bicyclic molecule , physics
Abstract High‐level non‐empirical calculations of carbon–carbon spin–spin coupling constants in a series of strained polycarbocycles have been carried out, in excellent agreement with available experimental data. The utmost importance of electronic correlation effects in this case has been demonstrated and it has been shown that the Second‐Order Polarization Propagator Approach (SOPPA) is an adequate method to account for those effects. It has been demonstrated that the most reliable basis sets to calculate J (C,C) at the SOPPA level are the correlation‐consistent basis sets of Dunning and co‐workers augmented with inner core s‐functions or decontracted in their s‐parts. The nature of the unusual bridgehead–bridgehead bonds in bicyclobutane and propellane in terms of s‐characters of bonding hybrids and also the hybridization effects in spiropentane are discussed based on the arguments derived from the current calculations of J (C,C) in the title compounds. The values of the unknown J (C,C) in propellane and spiropentane are predicted with high reliability. Copyright © 2003 John Wiley & Sons, Ltd.