Adducts of rhodium(II) tetraacetate with some nitrogenous organic ligands: Application of natural abundance 15N and 13C CPMAS NMR spectroscopy

Adducts of rhodium(II) tetraacetate with some nitrogenous organic ligands: 1-azabicyclo[2,2,2]octane 1, 1,2-diazabicyclo[2,2,2]octane 2, pyrazine 3, pyrimidine 4, [1,3,5]triazine 5 and 1,3,5,7-tetraazatricyclo[3,3,1,13,7]decane 6 have been investigated by means of natural abundance 13C and 15N CPMAS nuclear magnetic resonance (NMR) spectroscopy. 1-Azabicyclo[2,2,2]octane 1 having one nitrogen atom in the molecule produces either the 1:1 or 1:2-adduct depending on the reagent molar ratio; some features of its 13C CPMAS NMR spectra suggest the dimeric structure of the 1:1-adduct. Multifunctional ligands having more than one nitrogen atom in a molecule yield the adducts insoluble in common organic solvents. Elemental analysis and NMR experiments have revealed that 1,2-diazabicyclo[2,2,2]octane, pyrazine, pyrimidine and [1,3,5]triazine produced adducts in the form of 1:1 polymeric chains. 1,3,5,7-tetraazatricyclo[3,3,1,13,7]decane yields the adduct containing ligand and metal salt in the molar ratio of 3:4. The 15N chemical shift change caused by the Rh-N bond formation (Δδ parameter) varies from ca. −9 ppm for aliphatic ligands to ca. −40 ppm for heteroaromatic species. The NMR findings have been supported by theoretical calculation (density functional calculation (DFT), LanLD2Z//B3LYB level) of molecular geometry, energy and chemical shieldings.