Square-planar Co(iii) in {O4} coordination: large ZFS and reactivity with ROS.

Square-planar Co(iii) in {O4} coordination: large ZFS and reactivity with ROS.
Chem Commun (Camb). 2018 Oct 08;:
Authors: Steele JL, Tahsini L, Sun C, Elinburg JK, Kotyk CM, McNeely J, Stoian SA, Dragulescu-Andrasi A, Ozarowski A, Ozerov M, Krzystek J, Telser J, Bacon JW, Golen JA, Rheingold AL, Doerrer LH
Abstract
Oxidation of distorted square-planar perfluoropinacolate Co compound [CoII(pinF)2]2-, 1, to [CoIII(pinF)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 χTIP = 1950 × 10-6 cm3 mol-1. This Co(iii) species, 2, reacts with ROS to oxidise two (pinF)2- ligands to form tetrahedral [CoII(Hpfa)4]2-, 3.
PMID: 30294742 [PubMed - as supplied by publisher]

Source: Chemical Communications - October 8, 2018 Category: Chemistry Authors: Steele JL, Tahsini L, Sun C, Elinburg JK, Kotyk CM, McNeely J, Stoian SA, Dragulescu-Andrasi A, Ozarowski A, Ozerov M, Krzystek J, Telser J, Bacon JW, Golen JA, Rheingold AL, Doerrer LH Tags: Chem Commun (Camb) Source Type: research