The 13C chemical shifts of methylcobalt(III) compounds with saturated amine ligands in cis positions to the methyl group and a monodentate ligand, L = CN-, NH3, NO2-, N 3-, H2O, or OH-, in the trans position are reported. The amine ligands used, 1,2-ethanediamine (en), 1,3-propanediamine (tn), N,N′-bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet), N,N′-bis(3-aminopropyl)-1,2-ethanediamine (3,2,3-tet), and 1,4,8,11-tetraazacyclotetradecane (cyclam), all exert an apparent cis influence on the 13C resonance signal of the coordinated methyl group. In the trans-[Co(en)2(CH3)(L)]n+ series the 15N resonance frequency of the coordinated en has also been measured. The influence of L on the en 15N chemical shifts is reverse the influence on the methyl 13C chemical shifts except in the case of L = NO2-, which affects a further deshielding of the amine nitrogen nucleus. The methyl 1JCH coupling constants in the trans-[Co(en)2(CH3)(L)]n+ series range from 128.09 Hz (L = CN-) to 134.11 Hz (L = H2O). The crystal structures of trans-[Co(en)2(CH3)(ClZnCl 3)], trans-[Co(3,2,3-tet)(CH3)(N3)]ClO 4, trans,trans-[(CH3)(en)2Co(CN)Co(en) 2(CH3)](PF6)3(CH3CN), and cis-[Co(en)2(CH3)(NH3)]ZnCl4 were determined from low-temperature X-ray diffraction data.
CITATION STYLE
Kofod, P., & Harris, P. (2004). NMR Spectroscopic and X-ray Crystallographic Study of Methylcobalt(III) Compounds with Saturated Amine Ligands. Inorganic Chemistry, 43(8), 2680–2688. https://doi.org/10.1021/ic0302682
Mendeley helps you to discover research relevant for your work.