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Free, publicly-accessible full text available March 1, 2025
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Coordination of 1-isopropyl-3,5-dipyridyl-6-oxoverdazyl to cobalt results in a dication best described in the solid state as a high spin cobalt( ii ) ion coordinated to two radical ligands with an S = 3/2 ground state. On dissolution in acetonitrile, the cobalt( ii ) form equilibrates with a cobalt( iii ) valence tautomer with an S = 1/2 ground state.more » « less
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The first transition metal mediated reductive coupling of diazoesters through the terminal nitrogens is reported. The resulting tetrazene-bridged bis(diazenylacetate) serves as a novel dinucleating ligand to iron(III). DFT calculations suggest that the reductive coupling takes place via a κ 2 intermediate, which induces significant radical character on the terminal nitrogen.more » « less
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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 .more » « less