Spectroscopy and Electrochemistry of Cobalt(III) Schiff Base Complexes

The structural, spectroscopic, and electrochemical properties of cobalt(III) derivatives of acacen (H 2 acacen = bis(acetylacetone) ethylenediimine) and related ligands have been investigated. Electronic structure calculations indicate that the absorption between 340 and 378 nm in Co III (acacen) spectra is attributable to the lowest π−π* intraligand charge-transfer transition. Equatorial ligand substitutions affect reduction potentials less than axial ligand changes, consistent with an electronic structural model in which d z 2 is populated in forming cobalt(II). The crystal structure of [Co(3-Cl-acacen)(NH 3 ) 2 ]BPh 4 has been determined: The compound crystallizes in the monoclinic space group P 2 1 / m (No. 11) with a = 9.720(2) Å, b = 18.142(4) Å, c = 10.046(2) Å, β = 100.11(3)°, D c = 1.339 g cm - 3, and Z = 2; the complex cation, [Co(3-Cl-acacen)(NH 3 ) 2 ] +, exhibits a slightly distorted octahedral coordination geometry. The distances between the cobalt atom and the two axial nitrogen donor atoms differ only slightly (1.960(6) and 1.951(6) Å) and are similar to Co−N distances found in cobalt−ammine complexes as well as the axial Co−N distances in [Co(acacen)(4-MeIm) 2 ]Br·1.5H 2 O; the latter compound crystallizes in the triclinic space group P 1̄ (No. 2) with a = 18.466(9) Å, b = 14.936(7) Å, c = 10.111(5)Å, α = 96.27(5)°, β = 94.12(5)°, γ = 112.78(5)°, D c = 1.447 g cm - 3, and Z = 4.