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7144253419
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note
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3tacn, 1,4,7-trimethyl-1,4,7-triazacyclononane; tmpa, tris(2-methylpyridyl)amine; bispicen, N,N′-bis(2-methylpyridyl)-1,2-ethanediamine; bispictn, N,N′- bis-(2-methylpyridyl)-1,3-propanediamine; Fe(Cp*)2, bis(pentamethylcyclo-pentadienyl)iron.
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7144262733
-
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Manuscript in preparation
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4 (1.20 V and -0.60 V versus SCE, respectively) have been observed in acetonitrile (Wright D. W.; Dubé, C. E.; Hagen, S. K.; Westmoreland, T. D.; Scott, M. J.; Armstrong, W. H. Manuscript in preparation).
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0000471119
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3 (Pal, S.; Chan, M.; Armstrong, W. H. J. Am. Chem. Soc. 1992, 114, 6398-6406) are the only identifiable high oxidation state products obtained. EPR experiments performed at 77 K do, however, show a six-line signal centered at g = 2.0 indicating the presence of an unidentified Mn(II) contaminant. The manganese contaminants were extracted from the crude reaction product as described.
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7144258713
-
-
Symbols: vs, very strong; s, strong; m, medium; w, weak; sh, shoulder
-
Symbols: vs, very strong; s, strong; m, medium; w, weak; sh, shoulder.
-
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58
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61
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7144260072
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note
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4.
-
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-
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62
-
-
7144228250
-
-
note
-
4]. The source of the H-atom is unknown at this time.
-
-
-
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63
-
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6844239208
-
-
3tacn for quantitative conversion of 1 to 2, other tertiary amines, including triethylamine, N,N,N′,N′N′-pentamethyldiethylenetriamine, quinuclidine, proton sponge, and DABCO, were effective reductants at somewhat higher concentrations. Triethylamine has been used previously in the reduction of inorganic complexes (Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877-910). The redox chemistry of tertiary amines has been extensively reviewed (Weinberg, N. L.; Weinberg H. R. Chem. Rev. 1968, 68, 449-522).
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33750831918
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3tacn for quantitative conversion of 1 to 2, other tertiary amines, including triethylamine, N,N,N′,N′N′-pentamethyldiethylenetriamine, quinuclidine, proton sponge, and DABCO, were effective reductants at somewhat higher concentrations. Triethylamine has been used previously in the reduction of inorganic complexes (Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877-910). The redox chemistry of tertiary amines has been extensively reviewed (Weinberg, N. L.; Weinberg H. R. Chem. Rev. 1968, 68, 449-522).
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7144256845
-
-
note
-
+ is found for wavelengths less than 400 nm. The spectrum shown in Figure 2 is in good agreement with that of an authentic spectrum of 2 prepared by bulk electrolysis.
-
-
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66
-
-
7144255160
-
-
note
-
4+ can exist in many possible isomeric forms, yet remarkably, only one is observed in the solid state or in solution.
-
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67
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7144257508
-
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py, which are trans to μ-O ligands
-
py, which are trans to μ-O ligands.
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68
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27544451886
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A reversible electron transfer is characterized by a separation of cathodic and anodic CV peak potentials of 59/n mV, quasi-reversibility is characterized by cathodic and anodic peak potentials separated by more than 59/n mV, and irreversibility by the disappearance of a reverse peak (n = the number of electrons). A reversible electron transfer is also distinguished by a peak cathodic current/peak anodic current ratio of 1.
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87
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7144255845
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B
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4, was determined by spectrophotometric titration with pyridinium triflate in acetonitrile (Dubé, C. E.; Armstrong, W. H. Unpublished work).
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2 exhibited degradation in aqueous solution by cyclic voltammetry at slower scan rates. Reproducible voltammograms of the coupled processes were collected at 500 mV/s. Voltammetry of aqueous solutions of 1 above pH about 12 was not possible because of complex degradation.
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a in water is 13 (vide supra). The conversion of 2 to 1 with protonation is under investigation.
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