Square-planar Co(iii) in {O4} coordination: large ZFS and reactivity with ROSElectronic supplementary information (ESI) available. CCDC 1407677 (2) and 1407676 (3). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8cc04464c

• Main Authors: Steele, Jennifer L, Tahsini, Laleh, Sun, Chen, Elinburg, Jessica K, Kotyk, Christopher M, McNeely, James, Stoian, Sebastian A, Dragulescu-Andrasi, Alina, Ozarowski, Andrew, Ozerov, M, Krzystek, J, Telser, Joshua, Bacon, Jeffrey W, Golen, James A, Rheingold, Arnold L, Doerrer, Linda H
• Format: Article
• ISSN: 1359-7345; 1364-548X
• DOI: 10.1039/c8cc04464c

Oxidation of distorted square-planar perfluoropinacolate Co compound [Co II (pin F ) 2 ] 2− , 1 , to [Co III (pin F ) 2 ] 1− , 2 , is reported. Rigidly square-planar 2 has an intermediate-spin, S = 1, ground state and very large zero-field splitting (ZFS) with D = 67.2 cm −1 ; | E | = 18.0 cm −1 , ( E / D = 0.27), g = 2.10, g | = 2.25 and χ TIP = 1950 × 10 −6 cm 3 mol −1 . This Co( iii ) species, 2 , reacts with ROS to oxidise two (pin F ) 2− ligands to form tetrahedral [Co II (Hpfa) 4 ] 2− , 3 . Oxidation of distorted square-planar perfluoropinacolate Co compound [Co II (pin F ) 2 ] 2− , 1 , to [Co III (pin F ) 2 ] 1− , 2 , is reported.