Preparation and infrared spectroelectrochemical studies of five-coordinate (por)Fe(OC(=O)R) compounds (por = TPP, OEP; R = CCl3, CH2Cl)

Nan Xu; Beiqi Yan; Dennis Awasabisah; Douglas R. Powell; George B. Richter-Addo

doi:10.1016/j.ica.2017.09.014

Preparation and infrared spectroelectrochemical studies of five-coordinate (por)Fe(OC(=O)R) compounds (por = TPP, OEP; R = CCl₃, CH₂Cl)

Nan Xu
, Beiqi Yan
, Dennis Awasabisah
, Douglas R. Powell
, George B. Richter-Addo

Division of Mathematics & Natural Sciences (Altoona)

Research output: Contribution to journal › Article › peer-review

Abstract

Three five-coordinate iron acetate porphyrin complexes, (por)Fe(OC(=O)R) (por = porphyrinato dianion; R = CCl₃, CH₂Cl), have been synthesized and characterized. The crystal structure of (TPP)Fe(OC(=O)CCl₃) (TPP = tetraphenylporphyrinato dianion) has been determined by X-ray crystallography. The redox behaviors of the (por)Fe(OC(=O)R) compounds have been investigated by cyclic voltammetry and infrared spectroelectrochemistry. Analysis of the data reveals that the first oxidations of the (por)Fe(OC(=O)R) compounds are porphyrin-centered processes to yield π-radical cations of the form (por^[rad]⁺)Fe(OC(=O)R), and the first reductions may facilitate the dissociation of the axial acetate ligands from the iron centers.

Original language	English (US)
Pages (from-to)	183-188
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	469
DOIs	https://doi.org/10.1016/j.ica.2017.09.014
State	Published - 2018

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2017.09.014

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@article{255c0a0ef3584fef9cef2d81b2f334c0,

title = "Preparation and infrared spectroelectrochemical studies of five-coordinate (por)Fe(OC(=O)R) compounds (por = TPP, OEP; R = CCl3, CH2Cl)",

abstract = "Three five-coordinate iron acetate porphyrin complexes, (por)Fe(OC(=O)R) (por = porphyrinato dianion; R = CCl3, CH2Cl), have been synthesized and characterized. The crystal structure of (TPP)Fe(OC(=O)CCl3) (TPP = tetraphenylporphyrinato dianion) has been determined by X-ray crystallography. The redox behaviors of the (por)Fe(OC(=O)R) compounds have been investigated by cyclic voltammetry and infrared spectroelectrochemistry. Analysis of the data reveals that the first oxidations of the (por)Fe(OC(=O)R) compounds are porphyrin-centered processes to yield π-radical cations of the form (por[rad]+)Fe(OC(=O)R), and the first reductions may facilitate the dissociation of the axial acetate ligands from the iron centers.",

author = "Nan Xu and Beiqi Yan and Dennis Awasabisah and Powell, \{Douglas R.\} and Richter-Addo, \{George B.\}",

note = "Funding Information: We are grateful to Penn State Univ. Altoona for support (to NX), and to the National Science Foundation (CHE-1566509 and CHE-1213674 to GBRA) for funding for this research. Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",

year = "2018",

doi = "10.1016/j.ica.2017.09.014",

language = "English (US)",

volume = "469",

pages = "183--188",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Preparation and infrared spectroelectrochemical studies of five-coordinate (por)Fe(OC(=O)R) compounds (por = TPP, OEP; R = CCl3, CH2Cl)

AU - Xu, Nan

AU - Yan, Beiqi

AU - Awasabisah, Dennis

AU - Powell, Douglas R.

AU - Richter-Addo, George B.

N1 - Funding Information: We are grateful to Penn State Univ. Altoona for support (to NX), and to the National Science Foundation (CHE-1566509 and CHE-1213674 to GBRA) for funding for this research. Publisher Copyright: © 2017 Elsevier B.V.

PY - 2018

Y1 - 2018

N2 - Three five-coordinate iron acetate porphyrin complexes, (por)Fe(OC(=O)R) (por = porphyrinato dianion; R = CCl3, CH2Cl), have been synthesized and characterized. The crystal structure of (TPP)Fe(OC(=O)CCl3) (TPP = tetraphenylporphyrinato dianion) has been determined by X-ray crystallography. The redox behaviors of the (por)Fe(OC(=O)R) compounds have been investigated by cyclic voltammetry and infrared spectroelectrochemistry. Analysis of the data reveals that the first oxidations of the (por)Fe(OC(=O)R) compounds are porphyrin-centered processes to yield π-radical cations of the form (por[rad]+)Fe(OC(=O)R), and the first reductions may facilitate the dissociation of the axial acetate ligands from the iron centers.

AB - Three five-coordinate iron acetate porphyrin complexes, (por)Fe(OC(=O)R) (por = porphyrinato dianion; R = CCl3, CH2Cl), have been synthesized and characterized. The crystal structure of (TPP)Fe(OC(=O)CCl3) (TPP = tetraphenylporphyrinato dianion) has been determined by X-ray crystallography. The redox behaviors of the (por)Fe(OC(=O)R) compounds have been investigated by cyclic voltammetry and infrared spectroelectrochemistry. Analysis of the data reveals that the first oxidations of the (por)Fe(OC(=O)R) compounds are porphyrin-centered processes to yield π-radical cations of the form (por[rad]+)Fe(OC(=O)R), and the first reductions may facilitate the dissociation of the axial acetate ligands from the iron centers.

UR - https://www.scopus.com/pages/publications/85029534314

UR - https://www.scopus.com/pages/publications/85029534314#tab=citedBy

U2 - 10.1016/j.ica.2017.09.014

DO - 10.1016/j.ica.2017.09.014

M3 - Article

AN - SCOPUS:85029534314

SN - 0020-1693

VL - 469

SP - 183

EP - 188

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Preparation and infrared spectroelectrochemical studies of five-coordinate (por)Fe(OC(=O)R) compounds (por = TPP, OEP; R = CCl₃, CH₂Cl)

Abstract

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