Intermetal coupling in [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) and in their dicationic and monocationic mixed-valence forms

Min Chul Chung, Xinhong Gu, Beth A. Etzenhouser, Anne Marie Spuches, Peter T. Rye, Sripriya K. Seetharaman, David J. Rose, Jon A Zubieta, Michael Sponsler

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Abstract

The butadienediyl-bridged complexes [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) (R = H, Me) and their radical cationic and dicationic forms have been prepared and characterized by cyclic voltammetry, electronic spectroscopy (UV-vis and near-IR), EPR, and X-ray crystallography (R = Me). Comparisons with each other and with the literature complexes [(η5-C5R 5)Fe(dppm)]2(μ-CH=CHCH=CH), [(η5-C 5Me5)Fe(dppe)]2(μ-C≡CC≡C), and [(η5-C5Me5)-Fe(dppe)] 2(μ-C(OMe)=CHCH=C(OMe)) have allowed for systematic evaluation of several structural variations (C5H5 vs C 5Me5, dppm vs dppe, μ-CH=CHCH=CH vs μ-C≡CC≡C, and μ-CH=CHCH=CH vs μ-C(OMe)=CHCH=C(OMe)) and their effects on spectra and electronic intermetal coupling. Some of the structural changes have opposite effects on Hab, the effective coupling parameter, and Kc, the comproportionation constant. The data for the mixed-valence cations are most consistent with electronic delocalization.

Original languageEnglish (US)
Pages (from-to)3485-3494
Number of pages10
JournalOrganometallics
Volume22
Issue number17
DOIs
StatePublished - Aug 18 2003

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X ray crystallography
Ultraviolet spectroscopy
Cyclic voltammetry
Paramagnetic resonance
Cations
methylidyne
valence
electronics
crystallography
cations
evaluation
spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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Intermetal coupling in [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) and in their dicationic and monocationic mixed-valence forms. / Chung, Min Chul; Gu, Xinhong; Etzenhouser, Beth A.; Spuches, Anne Marie; Rye, Peter T.; Seetharaman, Sripriya K.; Rose, David J.; Zubieta, Jon A; Sponsler, Michael.

In: Organometallics, Vol. 22, No. 17, 18.08.2003, p. 3485-3494.

Research output: Contribution to journalArticle

Chung, Min Chul ; Gu, Xinhong ; Etzenhouser, Beth A. ; Spuches, Anne Marie ; Rye, Peter T. ; Seetharaman, Sripriya K. ; Rose, David J. ; Zubieta, Jon A ; Sponsler, Michael. / Intermetal coupling in [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) and in their dicationic and monocationic mixed-valence forms. In: Organometallics. 2003 ; Vol. 22, No. 17. pp. 3485-3494.
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abstract = "The butadienediyl-bridged complexes [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) (R = H, Me) and their radical cationic and dicationic forms have been prepared and characterized by cyclic voltammetry, electronic spectroscopy (UV-vis and near-IR), EPR, and X-ray crystallography (R = Me). Comparisons with each other and with the literature complexes [(η5-C5R 5)Fe(dppm)]2(μ-CH=CHCH=CH), [(η5-C 5Me5)Fe(dppe)]2(μ-C≡CC≡C), and [(η5-C5Me5)-Fe(dppe)] 2(μ-C(OMe)=CHCH=C(OMe)) have allowed for systematic evaluation of several structural variations (C5H5 vs C 5Me5, dppm vs dppe, μ-CH=CHCH=CH vs μ-C≡CC≡C, and μ-CH=CHCH=CH vs μ-C(OMe)=CHCH=C(OMe)) and their effects on spectra and electronic intermetal coupling. Some of the structural changes have opposite effects on Hab, the effective coupling parameter, and Kc, the comproportionation constant. The data for the mixed-valence cations are most consistent with electronic delocalization.",
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