Extensive Redox Non-Innocence in Iron Bipyridine-Diimine Complexes: a Combined Spectroscopic and Computational Study

Ranjeesh Thenarukandiyil; Eno Paenurk; Anthony Wong; Natalia Fridman; Amir Karton; Raanan Carmieli; Gabriel Ménard; Renana Gershoni-Poranne; Graham de Ruiter

doi:10.1021/acs.inorgchem.1c02925

Extensive Redox Non-Innocence in Iron Bipyridine-Diimine Complexes: a Combined Spectroscopic and Computational Study

Ranjeesh Thenarukandiyil
, Eno Paenurk
, Anthony Wong
, Natalia Fridman
, Amir Karton
, Raanan Carmieli
, Gabriel Ménard
, Renana Gershoni-Poranne
, Graham de Ruiter

Faculty of Science, Ag, Business and Law

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

9 Citations (Scopus)

Abstract

Metal-ligand cooperation is an important aspect in earth-abundant metal catalysis. Utilizing ligands as electron reservoirs to supplement the redox chemistry of the metal has resulted in many new exciting discoveries. Here, we demonstrate that iron bipyridine-diimine (BDI) complexes exhibit an extensive electron-transfer series that spans a total of five oxidation states, ranging from the trication [Fe(BDI)]³⁺ to the monoanion [Fe(BDI]^-1. Structural characterization by X-ray crystallography revealed the multifaceted redox noninnocence of the BDI ligand, while spectroscopic (e.g., ⁵⁷Fe Mössbauer and EPR spectroscopy) and computational studies were employed to elucidate the electronic structure of the isolated complexes, which are further discussed in this report.

Original language	English
Pages (from-to)	18296-18306
Journal	Inorganic Chemistry
Volume	60
Issue number	23
Early online date	17 Nov 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c02925
Publication status	Published - 6 Dec 2021

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10.1021/acs.inorgchem.1c02925

https://hdl.handle.net/1959.11/47456Licence: CC BY

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title = "Extensive Redox Non-Innocence in Iron Bipyridine-Diimine Complexes: a Combined Spectroscopic and Computational Study",

abstract = "Metal-ligand cooperation is an important aspect in earth-abundant metal catalysis. Utilizing ligands as electron reservoirs to supplement the redox chemistry of the metal has resulted in many new exciting discoveries. Here, we demonstrate that iron bipyridine-diimine (BDI) complexes exhibit an extensive electron-transfer series that spans a total of five oxidation states, ranging from the trication [Fe(BDI)]3+ to the monoanion [Fe(BDI]-1. Structural characterization by X-ray crystallography revealed the multifaceted redox noninnocence of the BDI ligand, while spectroscopic (e.g., 57Fe M{\"o}ssbauer and EPR spectroscopy) and computational studies were employed to elucidate the electronic structure of the isolated complexes, which are further discussed in this report.",

author = "Ranjeesh Thenarukandiyil and Eno Paenurk and Anthony Wong and Natalia Fridman and Amir Karton and Raanan Carmieli and Gabriel M{\'e}nard and Renana Gershoni-Poranne and \{de Ruiter\}, Graham",

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doi = "10.1021/acs.inorgchem.1c02925",

language = "English",

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TY - JOUR

T1 - Extensive Redox Non-Innocence in Iron Bipyridine-Diimine Complexes

T2 - a Combined Spectroscopic and Computational Study

AU - Thenarukandiyil, Ranjeesh

AU - Paenurk, Eno

AU - Wong, Anthony

AU - Fridman, Natalia

AU - Karton, Amir

AU - Carmieli, Raanan

AU - Ménard, Gabriel

AU - Gershoni-Poranne, Renana

AU - de Ruiter, Graham

PY - 2021/12/6

Y1 - 2021/12/6

N2 - Metal-ligand cooperation is an important aspect in earth-abundant metal catalysis. Utilizing ligands as electron reservoirs to supplement the redox chemistry of the metal has resulted in many new exciting discoveries. Here, we demonstrate that iron bipyridine-diimine (BDI) complexes exhibit an extensive electron-transfer series that spans a total of five oxidation states, ranging from the trication [Fe(BDI)]3+ to the monoanion [Fe(BDI]-1. Structural characterization by X-ray crystallography revealed the multifaceted redox noninnocence of the BDI ligand, while spectroscopic (e.g., 57Fe Mössbauer and EPR spectroscopy) and computational studies were employed to elucidate the electronic structure of the isolated complexes, which are further discussed in this report.

AB - Metal-ligand cooperation is an important aspect in earth-abundant metal catalysis. Utilizing ligands as electron reservoirs to supplement the redox chemistry of the metal has resulted in many new exciting discoveries. Here, we demonstrate that iron bipyridine-diimine (BDI) complexes exhibit an extensive electron-transfer series that spans a total of five oxidation states, ranging from the trication [Fe(BDI)]3+ to the monoanion [Fe(BDI]-1. Structural characterization by X-ray crystallography revealed the multifaceted redox noninnocence of the BDI ligand, while spectroscopic (e.g., 57Fe Mössbauer and EPR spectroscopy) and computational studies were employed to elucidate the electronic structure of the isolated complexes, which are further discussed in this report.

U2 - 10.1021/acs.inorgchem.1c02925

DO - 10.1021/acs.inorgchem.1c02925

M3 - Article

C2 - 34787414

SN - 0020-1669

VL - 60

SP - 18296

EP - 18306

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 23

ER -

Extensive Redox Non-Innocence in Iron Bipyridine-Diimine Complexes: a Combined Spectroscopic and Computational Study

Abstract

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