Electrochemistry of Iron and Ruthenium Flyover Bridge Complexes

Domenico Osella; Mauro Botta; Roberto Gobetto; Franco Laschi; Piero Zanello

doi:10.1021/om00092a008

Electrochemistry of Iron and Ruthenium Flyover Bridge Complexes

Domenico Osella, Mauro Botta, Roberto Gobetto, Franco Laschi, Piero Zanello

Risultato della ricerca: Contributo su rivista › Articolo in rivista › peer review

Abstract

The redox chemistry of dimetallacycloheptadiene (flyover bridge) complexes M₂(CO)₆[C(R)═C(R')-COC(R“)═(R')] (M = Fe or Ru) has been investigated by electrochemical and spectroscopic techniques. For the Fe₂(CO)₆[(PhC₂Ph)₂CO] derivative the bulk of the data indicates a sequence of electrochemical events involving the formation of the monoanion and its decomposition to solvated [Fe(CO)₃]^- and Fe-(CO)₃[(PhC₂Ph)₂CO] fragments, which are able to recombine together on electrochemical or chemical reoxidation giving back the parent complex. Electron paramagnetic resonance features of electroreduced solutions of ¹³CO-enriched sample of Fe₂(CO)₆[(PhC₂Ph)₂CO] and its monophosphine derivative Fe₂-(CO)₅(PPh)₃[(PhC₂Ph)₂CO] lend support to the proposed mechanism. The influence of the dienone substituents, R, as well as the effect of the replacement of group V (15) donor ligands for CO on the trend of the electrode potentials is discussed.

Lingua originale	Inglese
pagine (da-a)	283-288
Numero di pagine	6
Rivista	Organometallics
Volume	7
Numero di pubblicazione	2
DOI	https://doi.org/10.1021/om00092a008
Stato di pubblicazione	Pubblicato - feb 1988
Pubblicato esternamente	Sì

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10.1021/om00092a008

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title = "Electrochemistry of Iron and Ruthenium Flyover Bridge Complexes",

abstract = "The redox chemistry of dimetallacycloheptadiene (flyover bridge) complexes M2(CO)6[C(R)═C(R')-COC(R“)═(R')] (M = Fe or Ru) has been investigated by electrochemical and spectroscopic techniques. For the Fe2(CO)6[(PhC2Ph)2CO] derivative the bulk of the data indicates a sequence of electrochemical events involving the formation of the monoanion and its decomposition to solvated [Fe(CO)3]- and Fe-(CO)3[(PhC2Ph)2CO] fragments, which are able to recombine together on electrochemical or chemical reoxidation giving back the parent complex. Electron paramagnetic resonance features of electroreduced solutions of 13CO-enriched sample of Fe2(CO)6[(PhC2Ph)2CO] and its monophosphine derivative Fe2-(CO)5(PPh)3[(PhC2Ph)2CO] lend support to the proposed mechanism. The influence of the dienone substituents, R, as well as the effect of the replacement of group V (15) donor ligands for CO on the trend of the electrode potentials is discussed.",

author = "Domenico Osella and Mauro Botta and Roberto Gobetto and Franco Laschi and Piero Zanello",

year = "1988",

month = feb,

doi = "10.1021/om00092a008",

language = "English",

volume = "7",

pages = "283--288",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - Electrochemistry of Iron and Ruthenium Flyover Bridge Complexes

AU - Osella, Domenico

AU - Botta, Mauro

AU - Gobetto, Roberto

AU - Laschi, Franco

AU - Zanello, Piero

PY - 1988/2

Y1 - 1988/2

N2 - The redox chemistry of dimetallacycloheptadiene (flyover bridge) complexes M2(CO)6[C(R)═C(R')-COC(R“)═(R')] (M = Fe or Ru) has been investigated by electrochemical and spectroscopic techniques. For the Fe2(CO)6[(PhC2Ph)2CO] derivative the bulk of the data indicates a sequence of electrochemical events involving the formation of the monoanion and its decomposition to solvated [Fe(CO)3]- and Fe-(CO)3[(PhC2Ph)2CO] fragments, which are able to recombine together on electrochemical or chemical reoxidation giving back the parent complex. Electron paramagnetic resonance features of electroreduced solutions of 13CO-enriched sample of Fe2(CO)6[(PhC2Ph)2CO] and its monophosphine derivative Fe2-(CO)5(PPh)3[(PhC2Ph)2CO] lend support to the proposed mechanism. The influence of the dienone substituents, R, as well as the effect of the replacement of group V (15) donor ligands for CO on the trend of the electrode potentials is discussed.

AB - The redox chemistry of dimetallacycloheptadiene (flyover bridge) complexes M2(CO)6[C(R)═C(R')-COC(R“)═(R')] (M = Fe or Ru) has been investigated by electrochemical and spectroscopic techniques. For the Fe2(CO)6[(PhC2Ph)2CO] derivative the bulk of the data indicates a sequence of electrochemical events involving the formation of the monoanion and its decomposition to solvated [Fe(CO)3]- and Fe-(CO)3[(PhC2Ph)2CO] fragments, which are able to recombine together on electrochemical or chemical reoxidation giving back the parent complex. Electron paramagnetic resonance features of electroreduced solutions of 13CO-enriched sample of Fe2(CO)6[(PhC2Ph)2CO] and its monophosphine derivative Fe2-(CO)5(PPh)3[(PhC2Ph)2CO] lend support to the proposed mechanism. The influence of the dienone substituents, R, as well as the effect of the replacement of group V (15) donor ligands for CO on the trend of the electrode potentials is discussed.

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U2 - 10.1021/om00092a008

DO - 10.1021/om00092a008

M3 - Article

SN - 0276-7333

VL - 7

SP - 283

EP - 288

JO - Organometallics

JF - Organometallics

IS - 2

ER -

Electrochemistry of Iron and Ruthenium Flyover Bridge Complexes

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