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• W2040883641 abstract "The electrochemical behavior of two mononuclear MnII bis-terpyridine complexes, [MnII(L)2]2+ (L = terpy (2,2′:6′,2′′-terpyridine) and tBu3-terpy (4,4′,4′′-tritert-butyl-2,2′:6′,2′′-terpyridine)), has been investigated in dry CH3CN. Under these conditions, the cyclic voltammograms of these complexes exhibit not only the well-known MnII/MnIII oxidation system but also a second metal-based oxidation one, corresponding to the MnIII/MnIV redox couple. These oxidative processes are located at E1/2 = +0.96 and +1.77 V vs Ag/Ag+ (+1.26 and +2.07 V vs SCE) for the terpy complex and E1/2 = +0.85 and +1.56 V vs Ag/Ag+ (+1.15 and +1.86 V vs SCE) for the tBu3-terpy derivative. The one-electron oxidized form of these complexes, [MnIII(L)2]3+, has been quantitatively generated by exhaustive electrolyses at E = 1.30 V, as previously observed in the case of the oxidation of [MnII(tolyl-terpy)2]2+ (tolyl-terpy = 4′-(4-Methylphenyl)-2,2′:6′,2′′-terpyridine) (Romain, S.; Duboc, C.; Neese, F.; Rivière, E.; Hanton, L. R.; Blackman, A. G.; Leprêtre, J.-C.; Deronzier, A.; Collomb, M.-N. Chem.—Eur. J. 2009, 15, 980−988). Further electrolyses at E = 1.65−1.80 V of [MnIII(L)2]3+ solutions have shown that the [MnIV(L)2]4+ species is only stable for L = tBu3-terpy because of the strong electron-donating properties of the tert-butyl substituents. These electrogenerated high-valent complexes are rare examples of mononuclear MnIII and MnIV complexes stabilized solely by neutral N ligands. They have been fully characterized in solution by UV−visible and electron paramagnetic resonance (EPR) spectroscopies. A detailed investigation of the EPR spectra of the [MnII(tBu3-terpy)2]2+ and [MnIV(tBu3-terpy)2]4+ has allowed the determination of the spin Hamiltonian parameters for both systems (for MnII: |D| = 0.059 cm−1; |E| = 0.014 cm−1; E/D = 0.259; gx = gy = gz = 2.00 and for MnIV: |D| = 1.33(6) cm−1; |E| = 0.36(4) cm−1; E/D = 0.27; gx = 1.96(4); gy = 1.97(4); gz = 1.98(4))." @default.
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• W2040883641 date "2009-03-05" @default.
• W2040883641 modified "2023-10-17" @default.
• W2040883641 title "Mononuclear Mn^III and Mn^IV Bis-terpyridine Complexes: Electrochemical Formation and Spectroscopic Characterizations" @default.
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• W2040883641 doi "https://doi.org/10.1021/ic8024342" @default.
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