ABSTRACT
The synthesis and structural characterization of the hitherto unknown parent Co(bz)2+ (bz=benzene) complex and several of its derivatives are described. Their synthesis starts either from a CoCO5+ salt, or directly from Co2 (CO)8 and a Ag+ salt. Stability and solubility of these complexes was achieved by using the weakly coordinating anions (WCAs) [Al(ORF )4 ]- and [F{Al(ORF )3 }2 ]- {RF =C(CF3 )3 } and the solvent ortho-difluorobenzene (o-DFB). The magnetic properties of Co(bz)2+ were measured and compared in the condensed and gas phases. The weakly bound Co(o-dfb)2+ salts are of particular interest for the preparation of further CoI salts, for example, the structurally characterized low-coordinate 12 valence electron Co(Pt Bu3 )2+ and Co(NHC)2+ salts.
ABSTRACT
Cobalt-benzene cluster ions of the form Co3(bz)n+ (n = 0-3) were produced in the gas phase, mass-selected, and cooled in a cryogenic ion trap held at 3-4 K. To explore ligand effects on cluster magnetic moments, these species were investigated with X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopy. XMCD spectra yield both the spin and orbital angular momenta of these clusters. Co3+ has a spin magnetic moment of µS = 6 µB and an orbital magnetic moment of µL = 3 µB. Co3(bz)+ and Co3(bz)2+ complexes were found to have spin and orbital magnetic moments identical to the values for ligand-free Co3+. However, coordination of the third benzene to form Co3(bz)3+ completely quenches the high spin state of the system. Density functional theory calculations elucidate the spin states of the Co3(bz)n+ species as a function of the number of attached benzene ligands, explaining the transition from septet to singlet for n = 0 â 3.
