Journal of the American Chemical Society p. 8419 - 8425 (1991)
Update date:2022-07-30
Topics:
Collins, Terrence J.
Powell, Richard D.
Slebodnick, Carla
Uffelman, Erich S.
The first crystallographically characterized neutral square-planar complex of cobalt in an oxidation state higher than 2+, Co(η44-1), is reported. Structural data for this new class of compounds indicate that the macrocycle in Co(η4-1) is Equation Presented X = Cl, Co(η4-1) X = H, Co(η4-2) X = MeO, Co(η4-3) noninnocent; however, EPR data in toluene at 5.9 K (S = 1/2; g1 = 2.558, g2 = 2.170, g3 = 2.017; A2 ≈ 15 G) show that the metal center is the primary reisdence site of the unpaired electron. Co(η4-1) is a stable, yet potent, oxidant which is soluble in benzene and slightly soluble in pentane. The Co(η4-1)/[CoIII(η4-1)]- couple is reversible and found at 0.550 V vs Fc+/Fc in CH2Cl2 (ca. 1.26 V vs NHE). Co(η4-1) slowly oxidized water, yielding H[CoIII(η4-1)], which may also be prepared by the reaction of [CoIII(η4-1)]- with HBF4. Both the redox and the acid/base chemistries of [CoIII(η4-1)]- are reversible. Electrochemical and EPR data are also presented for Co(η4-2) and Co(η4-3).
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