Compounds with Symmetrical Tricobalt Chains Wrapped by Dipyridylamide Ligands and Cyanide or Isothiocyanate Ions as Terminal Ligands

Three new linear compounds of the type Co3(dpa)4X2, where dpa is the anion of di(2-pyridyl)amine and X is NCS- (5), CN- (6), and N(CN)2- (7), have been prepared, and their structures and magnetic behavior have been studied. In all of them, including three different solvates of 5, the Co3 chains are symmetrical with Co−Co distances of ca. 2.31−2.32 Å. The appearance of four lines in the 1H NMR spectra of the three compounds is also consistent with a symmetrical structure in solution. For all compounds, the magnetic behavior is quite similar with μeff of ca. 1.9−2.0 μB at temperatures between 1.8 and 200 K. As the temperature increases, the effective moments increase gradually, but since saturation is not reached, even at 400 K, the high-spin state cannot be assigned.