X-ray structure and spectroscopic characterization of divalent dinuclear cobalt complexes containing carboxylate- and phosphodiester- auxiliary bridges

Abstract

Two dinuclear spin-coupled divalent cobalt complexes, [Co 2(P1-O)(μ 2-OAc)](ClO 4) 2, ( 1) and [Co 2(P1-O)(μ 2-BNPP)](ClO 4) 2, ( 2) containing μ-1,3 acetate (OAc) and bis(4-nitrophenyl)phosphate (BNPP) auxiliary bridges, respectively, were synthesized by the reaction of a classic dinucleating ligand, P1–OH with cobalt(II) perchlorate in presence of acetic acid/bis(4-nitrophenyl)phosphate. They were characterized by single crystal X-ray diffraction, to show a trigonal bipyramidal geometry around each cobalt center and the intervening bridging atoms that are responsible for spin-transfer between the two divalent cobalt centers; the alkoxo oxygen donor occupies an equatorial position, and the auxiliary ligand oxygens (OAc/BNPP) occupy the axial positions. Solution state magnetic moment measurement together with UV–Vis/NIR spectra revealed a high-spin ground state ( S = 3/2) for Co(II) in these compounds. Complexes 1 and 2 show interesting 1H NMR spectral features of resonances with relatively narrower linewidths in conjunction with a sizable chemical shift dispersion of −5 and 265 ppm. Complex 2 containing the bis(4-nitrophenyl)phosphate auxiliary bridge showed narrower spectral window than complex 1 that has the acetate auxiliary bridge.