I. SYNTHESES OF IRON AND COBALT COMPLEXES WITH LIGANDS CONTAINING SILICON-NITROGEN BONDS. II. INTERNAL MOTIONS OF N-ORGANOSILYL KETIMINES.

摘要

The report presents results on two research programs,one on inorganic synthesis and one on structural study by means of broad-line NMR,which were pursued simultaneously during the year ending August 31, 1968. The first had to do with the synthesis of compounds of the transition metals containing organosilicon groups. Organosilyl amines were used as electrondonor ligands to form six new stable coordination compounds of iron and cobalt. The second project concerned the structures and behavior of five new compounds prepared last year,all with C=N-Si linkages (plus one additional compound with C=N-C linkage,for comparison). Earlier examination of the UV absorption spectra of these compounds had shown that there is little d pi - p pi interaction between the nitrogen and silicon,because the C=N-Si sequence is not linear but bent at an angle of 120deg. The spectra were obtained,and calculation of line widths and second moments showed that intramolecular motion in all five organosilicon compounds was hindered more than in the organic compound,and that one of the five (the only one which had an Si-N-C=N-Si structure) had a much more persistent restriction of motion with rise of temperature than the others. (Author)