Intermolecular Hydrogen Bonding in Protonated Diacidocobaloximes

The protonated diacidocobaloximes Co(dmgH)(dmgH2)(X)(Y), where X = Y = Cl^-, X = Y = SCN^-, X = Y = CN^-, or X = SCN^- and Y = CN^-, have been shown from their infrared spectra to crystallize in such a way that intermolecular hydrogen bonding occurs. This intermolecular association involves the hydroxyl group formed by the protonation of the oxime oxygen of one molecule and (1) the Cl^- ligand in Co(dmgH)(dmgH2)(Cl)2, (2) the S-bonded thiocyanate ligand in Co(dmgH)(dmgH2)(SCN)(NCS), (3) the cyano ligand of Co(dmgH)dmgH2)(SCN)(CN), and (4) one of the cyano ligands in Co(dmgH)(dmgH2)(CN)2. The linkage isomer for the thiocyanate containing compounds has been identified in the solid state and solution. The relative basicities of the free end of the coordinated cyanide, thiocyanate, and isothiocyanate are found to be in the order CN^-> SCN^-≫ NCS^-. © 1975, American Chemical Society. All rights reserved.

Duke Scholars

Author Alvin L. Crumbliss Chemistry