Solid-state 13C NMR and quantum chemical investigation of metal diene complexes

This paper presents novel measurements and calculations of the olefinic 13C chemical shift tensor principal values in several metal diene complexes. The experimental values and the calculations show shifts as large as 70 ppm with respect to the values in the parent olefinic compounds. These shifts are highly anisotropic, with the largest ones observed in the less shielded principal components and the smallest ones in the most shielded principal components of the tensor. The orientations of the principal components of the tensors remain, within 10°, at their directions in ethylene and other olefinic compounds. The calculations, performed using the GIAO method and the LanDZ pseudopotential basis set, show good agreement with the experiments, and were used to establish definite evidence for the existence of a Cl‐bridge structure in the bicyclo[2.2.1]hepta‐2,5‐diene (BCHD)dichlororuthenium(II) polymer. Copyright © 2007 John Wiley & Sons, Ltd.