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Updated: Aug 24, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
NMR spectroscopic and X-ray crystallographic study of methylcobalt(III) compounds with saturated amine ligands
1Department of Life Sciences and Chemistry, Roskilde University, P.O. Box 260, DK-4000 Roskilde, Denmark. pkofod@ruc.dk
Abstract:
The (13)C chemical shifts of methylcobalt(III) compounds with saturated amine ligands in cis positions to the methyl group and a monodentate ligand, L = CN(-), NH(3), NO(2)(-), N(3)(-), H(2)O, 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 (13)C resonance signal of the coordinated methyl group. In the trans-[Co(en)(2)(CH(3))(L)](n+) series the (15)N resonance frequency of the coordinated en has also been measured. The influence of L on the en (15)N chemical shifts is reverse the influence on the methyl (13)C chemical shifts except in the case of L = NO(2)(-), which affects a further deshielding of the amine nitrogen nucleus. The methyl (1)J(CH) coupling constants in the trans-[Co(en)(2)(CH(3))(L)](n+) series range from 128.09 Hz (L = CN(-)) to 134.11 Hz (L = H(2)O). The crystal structures of trans-[Co(en)(2)(CH(3))(ClZnCl(3))], trans-[Co(3,2,3-tet)(CH(3))(N(3))]ClO(4), trans,trans-[(CH(3))(en)(2)Co(CN)Co(en)(2)(CH(3))](PF(6))(3)(CH(3)CN), and cis-[Co(en)(2)(CH(3))(NH(3))]ZnCl(4) were determined from low-temperature X-ray diffraction data.
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