ESR study of irradiated pentacyanonitrosyl cobaltate(II)

Manoharan, P. T. ; Subramanian, S. ; Rogers, Max T. (1974) ESR study of irradiated pentacyanonitrosyl cobaltate(II) Journal of Coordination Chemistry, 3 (4). pp. 293-299. ISSN 0095-8972

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An ESR study of γ-irradiated pentacyanonitrosyl cobaltate (II) shows the presence of two paramagnetic species. One, with g‖ =2.005, g‖ =2.172, A‖ 81.3 and A‖ =-26.2 × 10−4 cm−1, is the well-known d7 species Co(CN)53-. The second shows g‖<‖g and much lower 59Co hyperfine interactions. The ESR parameters are shown to be consistent with those predicted for the species [Co(CN)5 NO]4- with C S symmetry, a bent Co–N–O bond, and a d 7 configuration with the odd electron in an a' orbital formed by mixing the cobalt d x –y 2 and d z 2 orbitals. Theoretical arguments are advanced to show that, in general, small metal hyperfine splittings in low symmetry ions do not necessarily establish that the unpaired electron is in a ligand-dominated orbital.

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