The synthesis, physical properties, and electron spin resonance of frozen solutions of CoTAAB(NO3)2 (TAAB = tetrabenzo[b,f,j,n] [1,5,9,13]tetraazacyclohexadecine) are reported. The spin Hamiltonian parameters were elucidated by simulation of spectra assuming axial g and 59Co hyperfine tensors and including nuclear quadrupole and Zeeman contributions. Electron spin resonance spectra in solvents such as methanol, acetone, and dimethylformamide are typical for a low spin complex (S = 1/2) and are nearly identical with [Formula: see text] and [Formula: see text]. In pyridine and quinoline a complex with a molar ratio solvent/ligand of 1:1 is formed with the solvent which gives [Formula: see text]and [Formula: see text] much closer to [Formula: see text]. In strong Lewis bases, such as piperidine, a 2:1 complex is formed and no esr signal is found. Evidence is presented to show that these 2:1 complexes with strong Lewis bases are S = 1/2 complexes with a low lying S = 3/2 state that is partially populated at room temperatures. This behaviour is accounted for in terms of a theory derived for a 2A1 ground state with a low lying quartet state which could become the ground state in strong basic solvents.