Multicenter bonding in organic chemistry. Geometry-sensitive 3c-2e bonding in (C...H...C) fragments of organic cations

This paper reports the application of a new general tool for the study of multicenter bonding, namely the so-called generalized population analysis, to the investigation of interesting geometry dependent variation of 3c-2e bonding in the (C...H...C) fragments of ingeniously designed organic cations I and II. This phenomenon was previously characterized by the correlation between experimental (1)H NMR chemical shifts of the central hydrogen in the (C...H...C) fragment and the changes in the corresponding C-H-C bond angle. The observed values of both chemical shifts and C-H-C angles are shown herein to correlate with the calculated 3-center bond indices but the dependence displays splitting into two separate lines according to the type of corresponding cation.