ELECTROCHEMISTRY OF IRON AND RUTHENIUM FLYOVER BRIDGE COMPLEXES

Domenico OSELLA; Mauro BOTTA; R GOBETTO; F LASCHI; P. ZANELLO

doi:10.1021/om00092a008

ELECTROCHEMISTRY OF IRON AND RUTHENIUM FLYOVER BRIDGE COMPLEXES

Domenico OSELLA
, Mauro BOTTA
, R GOBETTO
, F LASCHI
, P. ZANELLO

Department of Science and Technological Innovation

Research output: Contribution to journal › Article › 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.

Original language	English
Pages (from-to)	283-288
Number of pages	6
Journal	Organometallics
Volume	7
Issue number	2
DOIs	https://doi.org/10.1021/om00092a008
Publication status	Published - 1988

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http://hdl.handle.net/11579/31238

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@article{7332ff4746b44ec3ae203fc4e5db7cd3,

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 R GOBETTO and F LASCHI and P. ZANELLO",

year = "1988",

doi = "10.1021/om00092a008",

language = "English",

volume = "7",

pages = "283--288",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - ELECTROCHEMISTRY OF IRON AND RUTHENIUM FLYOVER BRIDGE COMPLEXES

AU - OSELLA, Domenico

AU - BOTTA, Mauro

AU - GOBETTO, R

AU - LASCHI, F

AU - ZANELLO, P.

PY - 1988

Y1 - 1988

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.

UR - https://iris.uniupo.it/handle/11579/31238

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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