Proton ENDOR study of copper(II) bis(dithiocarbamate)

The proton hyperfine coupling tensors of the methylene protons in methyl-deuterated copper(II) bis(N,N-diethyldithiocarbamate) in a diamagnetic host crystal of the corresponding nickel complex have been measured by ENDOR spectroscopy. Two intermolecular and all four intramolecular proton coupling tensors could be determined. With the aid of spin densities, obtained from extended Hückel molecular orbital calculations, the anisotropic part of the tensors can be reproduced quantitatively, taking into account all two- and three-centre contributions. Comparison of the transition frequencies which are computed from the theoretical tensors with the experimental transitions enables the tracing of another five tensors which cannot be completely determined experimentally.