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Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction

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1999

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Geiger, William

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Organometallics. 1999, 18(10), pp. 1827-1833. ISSN 0276-7333. Available under: doi: 10.1021/om9809724

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The redox reactions of CpFe(η5-P5) (1; Cp = η5-C5Me5) have been characterized in nonaqueous solvents by electrochemical methods. As anticipated by analogy with ferrocene, 1 may be both oxidized and reduced in one-electron processes. Both processes are irreversible by cyclic voltammetry but reversible by bulk electrolysis. In CH2Cl2 complex 1 oxidizes initially to 17-electron 1+ (Ep,a = 0.57 V vs Fc), which rapidly equilibrates to give the dimeric dication [12]2+. An ESR spectrum attributed to 1+ is consistent with a d5 iron sandwich complex. A dimerization rate constant for 1+ of kD(17) = 1.4 × 104 M-1 s-1 was determined from cyclic voltammetry (CV) data. The dimeric dication quantitatively re-forms neutral 1 upon rereduction. Complex 1 undergoes reduction (E1/2 = −2.00 V) to 19-electron 1-, which also appears to dimerize in THF; kD(19) = ca. 6 × 105 M-1 s-1. Reoxidation of the diamagnetic dimer [12]2- regenerates 1. The shifts in potential induced when replacing a cyclopentadienyl ring by a pentaphosphacyclopentadienyl ring, explicable in terms of the weaker electron-donating ability of the latter, are greater for the reductions than the oxidations, implying an increased P5 character to the LUMO of 1 compared to the HOMO. Possible structures of the dimeric ions are discussed in terms of known structural analogues and previously published molecular orbital descriptions.

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540 Chemie

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ISO 690WINTER, Rainer F., William GEIGER, 1999. Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction. In: Organometallics. 1999, 18(10), pp. 1827-1833. ISSN 0276-7333. Available under: doi: 10.1021/om9809724
BibTex
@article{Winter1999Elect-13864,
  year={1999},
  doi={10.1021/om9809724},
  title={Electron-Transfer Properties of Cp*FeP5: Evidence for Dimerization Reactions following both Oxidation and Reduction},
  number={10},
  volume={18},
  issn={0276-7333},
  journal={Organometallics},
  pages={1827--1833},
  author={Winter, Rainer F. and Geiger, William}
}
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    <dcterms:abstract xml:lang="eng">The redox reactions of Cp*Fe(η5-P5) (1; Cp* = η5-C5Me5) have been characterized in nonaqueous solvents by electrochemical methods. As anticipated by analogy with ferrocene, 1 may be both oxidized and reduced in one-electron processes. Both processes are irreversible by cyclic voltammetry but reversible by bulk electrolysis. In CH2Cl2 complex 1 oxidizes initially to 17-electron 1+ (Ep,a = 0.57 V vs Fc), which rapidly equilibrates to give the dimeric dication [12]2+. An ESR spectrum attributed to 1+ is consistent with a d5 iron sandwich complex. A dimerization rate constant for 1+ of kD(17) = 1.4 × 104 M-1 s-1 was determined from cyclic voltammetry (CV) data. The dimeric dication quantitatively re-forms neutral 1 upon rereduction. Complex 1 undergoes reduction (E1/2 = −2.00 V) to 19-electron 1-, which also appears to dimerize in THF; kD(19) = ca. 6 × 105 M-1 s-1. Reoxidation of the diamagnetic dimer [12]2- regenerates 1. The shifts in potential induced when replacing a cyclopentadienyl ring by a pentaphosphacyclopentadienyl ring, explicable in terms of the weaker electron-donating ability of the latter, are greater for the reductions than the oxidations, implying an increased P5 character to the LUMO of 1 compared to the HOMO. Possible structures of the dimeric ions are discussed in terms of known structural analogues and previously published molecular orbital descriptions.</dcterms:abstract>
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