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Indirect nuclear spin–spin coupling constants in 1,2-diboretane-3-ylidene, a homoaromatic system with π and σ 3c/2e bonds. Comparison of experimental data with calculations using density functional theory (DFT)

✍ Scribed by Bernd Wrackmeyer; Armin Berndt


Publisher
John Wiley and Sons
Year
2004
Tongue
English
Weight
182 KB
Volume
42
Category
Article
ISSN
0749-1581

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✦ Synopsis


Abstract

The non‐classical 1,2‐diboretane‐3‐ylidene 1a was studied by ^13^C and ^29^Si NMR spectroscopy in order to obtain coupling constants ^1^J(^13^C,^11^B) and ^1^J(^29^Si,^13^C). The magnitudes of ^1^J(^13^C,^11^B) were deduced from linewidth measurements in low‐temperature ^13^C and ^11^B NMR spectra. Calculation of the coupling constants for model compounds related to 1a, using DFT methods based on optimized geometries [B3LYP/6–311+G(d,p)], gave data in agreement with the experiments. Furthermore, the calculations predict for the first time a negative sign of ^1^J(^13^C,^11^B) which mirrors the bonding situation in 1 as described by theory. Copyright © 2004 John Wiley & Sons, Ltd.