Metal-assisted reactions. Part 29. Structure and hydrogenolysis of C-N bonds in derivatives of aromatic amines. Bond length and electronegativity changes from X-ray crystallographic data

Pseudosaccharyl and phenyltetrazolyl derivatives 1-6 were prepared with the aim of weakening the originally strong C-N bond in aromatic amines and facilitating its hydrogenolysis. Structural analyses of the amines 1-6 by H-1 and C-13 NMR spectroscopy and X-ray diffraction methods have revealed major changes in C-N bond lengths on derivatization as a result of changes in conjugation. These changes are discussed in relation to the observed reactivity of compounds 1-6 towards catalytic and non-catalytic C-N bond hydrogenolysis.