On the positronium spin conversion reactions caused by some macrocyclic Co complexes

The rate constants, k_CR, of ortho- into para-positronium (o-Ps→p-Ps) spin conversion reactions, CR, caused by the high-spin [Co^IIsep]²⁺, [Co^IIdinosar]²⁺ and [Co^IIdiamsar]²⁺ macrocyclic complexes and also by high-spin [Co^II sen]²⁺ tripod complex were measured at several temperatures. The delocalizations, β, of Co^II unpaired electrons, promoted by the mentioned ligands, were determined by using the previously established correlations between k_CR and the electron delocalization β of unpaired metal electrons. β is given by the ratio between the Racah inter-electronic repulsion parameters of complexes, B, and that of the free ions, B₀. The β values are compared with those of the Co^II complexes with en (1,2-ethanediamine), pn (1,2 propanediamine) and dien (2,2′ diamino diethylamine) ligands. The k_CR rate constants are also compared with those of the Ps oxidation reactions, OR, promoted by the corresponding Co^III complexes. It is concluded that, unlike OR's, the CR's do not occur by formation of hepta-coordinate adducts with Ps atoms.