An electron transfer series of octahedral chromium complexes containing a redox non-innocent α-diimine ligandElectronic supplementary information (ESI) available: Preparative and crystallographic and spectroscopic data. CCDC 1000091 and 1000092. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4cc03332a

An electron-transfer series of octahedral α-diimine complexes [( H L Cy ) 3 Cr] n + (BARF) n ( n = 2, 1, 0) has been synthesized and crystallographically characterized. Cyclic voltammetry indicated additional formation of [( H L Cy ) 3 Cr] 3+ . The molecular structures suggested that all redox processes were ligand-based. Magnetic moments were consistent with spin ground states of S = 0 for [ H L Cy 3 Cr] 0 , S = 1/2 for [ H L Cy 3 Cr] +1 , and S = 1 for [ H L Cy 3 Cr] +2 . The experimental data is consistent with chromium maintaining the +III oxidation state throughout, while being coordinated by varying numbers of neutral diimines ( H L Cy ) and diimine radical anions ( H L Cy &z.rad; − ). An electron-transfer series of octahedral α-diimine complexes [( H L Cy ) 3 Cr] n + (BARF) n ( n = 2, 1, 0) has been synthesized and crystallographically characterized.