Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes

Accompanied by a change in color from red to black, the enantiomorphic phases of cobalt complexes chiral salen ligand (L2?, Co(L)·CS2, and Co(L) (L = LS,S or LR,R)) chemisorb NO (g) at atmospheric pressure rt over hours for CS2 solvated phase, within seconds desolvated phase. is installed as an axial nitrosyl ligand. Aligned but unconnected voids desorbed Co(LR,R)·CS2 structure indicate conduits directional desorption reversible sorption NO, which occur without loss crystallinity. Vibrational circular dichroism (VCD) spectra have been recorded both hands LH2, Zn(L), Co(L), Co(NO)(L), Co(NO)(L)·CS2, revealing significant differences between solution-state solid-state spectra. Chiral induction enables detection ?NO band condensed states, surprisingly also achiral lattice solvent (CS2 (?CS 1514 cm?1)) VCD. Solution-state paramagnetic Co(II) complex shows nearly 10-fold enhancement more extensive inversion polarity vibrations dominant VCD bands compared diamagnetic compounds. This less pronounced when there are fewer inversions solid state