Paramagnetic Complexes of Expanded Cage Amine Ligands
- 18 February 2026
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 65 (8) , 4528-4537
Abstract
The synthesis and characterization of complexes of the macrobicyclic ligand Me8tricosane (1,5,5,9,13,13,20,20-octamethyl-3,7,11,15,18,22-hexaazabicyclo-[7.7.7]tricosane) with Ni(II) and Mn(II) are reported, along with further details of the synthesis and characterization of complexes of Mn(II) and Cr(III) with the related ligand Me5tricosane (1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]tricosane). X-ray structural analysis of (H3O)[Cr(Me5tricosane)]Cl4·3H2O revealed the presence of longer Cr-N bonds than in comparable Cr(III) hexaamine complexes, but this was accompanied by modest alterations to electronic spectroscopy and electrochemical behavior. Both Me5tricosane and Me8tricosane formed Mn(II) complexes which exhibited magnetic and electronic properties typical of high spin d5 systems. The solid-state structures of [Mn(Me5tricosane)](NO3)2·1.5H2O and [Mn(Me8tricosane)]Cl2·3H2O revealed a distorted trigonal prismatic MnN6 chromophore with longer Mn-N bonds than in similar Mn(II) complexes, and both [Mn(Me5tricosane)]2+ and [Mn(Me8tricosane)]2+ exhibited irreversible redox chemistry in cyclic voltammetry experiments. X-ray crystallographic analysis of [Ni(Me8tricosane)](NO3)2·H2O revealed remarkably long Ni(II)-N bonds, resulting in an unusual blue color for a Ni(II)N6 complex.Keywords
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