Synthesis and Electrocatalytic Activity of [FeFe]-Hydrogenase Model Complexes with Non-Innocent Chelating Nitrogen-Donor Ligands

Souvik Roy, Joseph A. Laureanti, Thomas L. Groy, Anne Katherine Jones

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

To probe the influence of redox non-innocent ligands on a well-known class of [FeFe]-hydrogenase models, three new asymmetrically disubstituted diiron complexes of the general formula (μ-SRS)[Fe(CO)3][Fe(CO)(N-N)] (SRS = propane-1,3-dithiolate (pdt) or benzene-1,2-dithiolate (bdt), and N-N = 2,2′-bipyridine (bipy) or 2,2′-bipyrimidine (bpym)) have been synthesized from their parent hexacarbonyls and characterized. The new complexes, (μ-pdt)Fe2(CO)42-bpym) (2), (μ-bdt)Fe2(CO)42-bipy) (3), and (μ-bdt)Fe2(CO)42-bpym) (4), were fully characterized by spectroscopic and electrochemical techniques, and the results are compared to those of a related complex, (μ-pdt)Fe2(CO)42-bipy) (1). The crystal structures of 2-4 show that, in each complex, the two iron units are in an eclipsed orientation, and the N-N ligand lies in the basal plane. IR spectra and electrochemical analyses indicate that electron density at the iron centers decreases in the order 1 > 2 > 3 > 4. Furthermore, compound 2 undergoes a ligand-centered reduction at the same potential that the hexacarbonyl precursor undergoes its first reduction. However, unlike the 2,2′-bipy derivatives 1 and 3, the 2,2′-bpym complexes 2 and 4 are not effective catalysts for electrochemical proton reduction from acetic acid.

Original languageEnglish
JournalEuropean Journal of Inorganic Chemistry
DOIs
Publication statusAccepted/In press - 2017

Fingerprint

Hydrogenase
Carbon Monoxide
Chelation
Nitrogen
Ligands
Propane
Benzene
Iron
Acetic Acid
Carrier concentration
Protons
Crystal structure
Derivatives
Catalysts

Keywords

  • Electrocatalysis
  • Electrochemistry
  • Hydrogen
  • N ligands
  • Redox chemistry
  • [FeFe]-hydrogenases

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{379bbc55d0644069bdf5a31f69fb276f,
title = "Synthesis and Electrocatalytic Activity of [FeFe]-Hydrogenase Model Complexes with Non-Innocent Chelating Nitrogen-Donor Ligands",
abstract = "To probe the influence of redox non-innocent ligands on a well-known class of [FeFe]-hydrogenase models, three new asymmetrically disubstituted diiron complexes of the general formula (μ-SRS)[Fe(CO)3][Fe(CO)(N-N)] (SRS = propane-1,3-dithiolate (pdt) or benzene-1,2-dithiolate (bdt), and N-N = 2,2′-bipyridine (bipy) or 2,2′-bipyrimidine (bpym)) have been synthesized from their parent hexacarbonyls and characterized. The new complexes, (μ-pdt)Fe2(CO)4(κ2-bpym) (2), (μ-bdt)Fe2(CO)4(κ2-bipy) (3), and (μ-bdt)Fe2(CO)4(κ2-bpym) (4), were fully characterized by spectroscopic and electrochemical techniques, and the results are compared to those of a related complex, (μ-pdt)Fe2(CO)4(κ2-bipy) (1). The crystal structures of 2-4 show that, in each complex, the two iron units are in an eclipsed orientation, and the N-N ligand lies in the basal plane. IR spectra and electrochemical analyses indicate that electron density at the iron centers decreases in the order 1 > 2 > 3 > 4. Furthermore, compound 2 undergoes a ligand-centered reduction at the same potential that the hexacarbonyl precursor undergoes its first reduction. However, unlike the 2,2′-bipy derivatives 1 and 3, the 2,2′-bpym complexes 2 and 4 are not effective catalysts for electrochemical proton reduction from acetic acid.",
keywords = "Electrocatalysis, Electrochemistry, Hydrogen, N ligands, Redox chemistry, [FeFe]-hydrogenases",
author = "Souvik Roy and Laureanti, {Joseph A.} and Groy, {Thomas L.} and Jones, {Anne Katherine}",
year = "2017",
doi = "10.1002/ejic.201700123",
language = "English",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",

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TY - JOUR

T1 - Synthesis and Electrocatalytic Activity of [FeFe]-Hydrogenase Model Complexes with Non-Innocent Chelating Nitrogen-Donor Ligands

AU - Roy, Souvik

AU - Laureanti, Joseph A.

AU - Groy, Thomas L.

AU - Jones, Anne Katherine

PY - 2017

Y1 - 2017

N2 - To probe the influence of redox non-innocent ligands on a well-known class of [FeFe]-hydrogenase models, three new asymmetrically disubstituted diiron complexes of the general formula (μ-SRS)[Fe(CO)3][Fe(CO)(N-N)] (SRS = propane-1,3-dithiolate (pdt) or benzene-1,2-dithiolate (bdt), and N-N = 2,2′-bipyridine (bipy) or 2,2′-bipyrimidine (bpym)) have been synthesized from their parent hexacarbonyls and characterized. The new complexes, (μ-pdt)Fe2(CO)4(κ2-bpym) (2), (μ-bdt)Fe2(CO)4(κ2-bipy) (3), and (μ-bdt)Fe2(CO)4(κ2-bpym) (4), were fully characterized by spectroscopic and electrochemical techniques, and the results are compared to those of a related complex, (μ-pdt)Fe2(CO)4(κ2-bipy) (1). The crystal structures of 2-4 show that, in each complex, the two iron units are in an eclipsed orientation, and the N-N ligand lies in the basal plane. IR spectra and electrochemical analyses indicate that electron density at the iron centers decreases in the order 1 > 2 > 3 > 4. Furthermore, compound 2 undergoes a ligand-centered reduction at the same potential that the hexacarbonyl precursor undergoes its first reduction. However, unlike the 2,2′-bipy derivatives 1 and 3, the 2,2′-bpym complexes 2 and 4 are not effective catalysts for electrochemical proton reduction from acetic acid.

AB - To probe the influence of redox non-innocent ligands on a well-known class of [FeFe]-hydrogenase models, three new asymmetrically disubstituted diiron complexes of the general formula (μ-SRS)[Fe(CO)3][Fe(CO)(N-N)] (SRS = propane-1,3-dithiolate (pdt) or benzene-1,2-dithiolate (bdt), and N-N = 2,2′-bipyridine (bipy) or 2,2′-bipyrimidine (bpym)) have been synthesized from their parent hexacarbonyls and characterized. The new complexes, (μ-pdt)Fe2(CO)4(κ2-bpym) (2), (μ-bdt)Fe2(CO)4(κ2-bipy) (3), and (μ-bdt)Fe2(CO)4(κ2-bpym) (4), were fully characterized by spectroscopic and electrochemical techniques, and the results are compared to those of a related complex, (μ-pdt)Fe2(CO)4(κ2-bipy) (1). The crystal structures of 2-4 show that, in each complex, the two iron units are in an eclipsed orientation, and the N-N ligand lies in the basal plane. IR spectra and electrochemical analyses indicate that electron density at the iron centers decreases in the order 1 > 2 > 3 > 4. Furthermore, compound 2 undergoes a ligand-centered reduction at the same potential that the hexacarbonyl precursor undergoes its first reduction. However, unlike the 2,2′-bipy derivatives 1 and 3, the 2,2′-bpym complexes 2 and 4 are not effective catalysts for electrochemical proton reduction from acetic acid.

KW - Electrocatalysis

KW - Electrochemistry

KW - Hydrogen

KW - N ligands

KW - Redox chemistry

KW - [FeFe]-hydrogenases

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U2 - 10.1002/ejic.201700123

DO - 10.1002/ejic.201700123

M3 - Article

AN - SCOPUS:85017447172

JO - Chemische Berichte

JF - Chemische Berichte

SN - 0009-2940

ER -