Nine structurally related paramagnetic acetylacetonato nickel(II) complexes: [Ni(acac)(2)] and trans-[Ni(acac)(2)(X)(2)]nH/D2O, X = H2O, D2O, NH3, MeOH, PMePh2, PMe2Ph, or [dppe](1/2), n = 0 or 1, dppe = 1,2-his(diphenylphosphino)ethane, as well as cis-[Ni(F-6-acac)(2)(D2O)(2)], F-6-acac = hexafluoroacetylonato, have been characterized by solid state C-13 MAS NMR spectroscopy. H-2 MAS NMR was used to probe the local hydrogen bonding network in [Ni(acac)(2)(D2O)(2)]D2O and cis-[Ni(F-6-acac)(2)(D2O)(2)]. The complexes serve to benchmark the paramagnetic shift, which can be associated with the resonances of atoms of the coordinated ligands. The methine (CH) and methyl (CH3) have characteristic combinations of the isotropic shift (delta) and anisotropy parameters (d, eta). The size of the anisotropy (d), which is the sum of the chemical shift anisotropy (CSA) and the paramagnetic electron-nuclei dipolar coupling, is much more descriptive than the isotropic shift. Moreover, the CSA is found to constitute up to one-third of the total anisotropy and should be taken into consideration when C-13 anisotropies are used for structure determination of paramagnetic materials. The C-13 MAS NMR spectra of trans[Ni(acac)(2)(PMe2Ph)(2)], trans-[Ni(acac)(2)(PMePh2)(2)], and the noncrystallographically characterized trans-[Ni(acac)(2)(dppe)], were assigned using these correlations. The complexes with L = H2O, D2O, NH3, and MeOH can be prepared by a series of solid state desorption and sorption reactions. Crystal structures for trans-[Ni(acac)(2)(NH3)(2)] and trans-[Ni(acac)(2)(PMePh2)(2)] are reported.
Inorganic Chemistry, 2014, Vol 53, Issue 1, p. 399-408