Zusammenfassung
The cluster complex (C5H5)(4)Fe4S4 formally contains Fe(III) and sulfide as constituents. In agreement with this assignment, the long-wavelength absorptions of the cluster are attributed to S2- to Fe(III) LMCT transitions. In solutions of acetonitrile, LMCT excitation of the cluster complex leads to a photoredox decomposition yielding Fe(II) and elemental sulfur. Upon a one-electron oxidation of ...
Zusammenfassung
The cluster complex (C5H5)(4)Fe4S4 formally contains Fe(III) and sulfide as constituents. In agreement with this assignment, the long-wavelength absorptions of the cluster are attributed to S2- to Fe(III) LMCT transitions. In solutions of acetonitrile, LMCT excitation of the cluster complex leads to a photoredox decomposition yielding Fe(II) and elemental sulfur. Upon a one-electron oxidation of (C5H5)(4)Fe4S4, the cation [(C5H5)(4)Fe4S4](+) is obtained, which is much more stable to water, air and light than the neutral parent cluster. Upon addition of [M(CN)(6)](4-) with MRu and Os to aqueous solutions of this cation, dark blue and violet colors, respectively, immediately develop, which are attributed to outer-sphere CT absorptions of the ion pairs [(C5H5)(4)Fe4S4](+)/(CN)(6)](4-). (C) 2015 Elsevier B.V. All rights reserved.
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