Metal: Vs. ligand protonation and the alleged proton-shuttling role of the azadithiolate ligand in catalytic H2 formation with FeFe hydrogenase model complexes

Alexander Aster, Shihuai Wang, Mohammad Mirmohades, Charlène Esmieu, Gustav Berggren, Leif Hammarström, Reiner Lomoth

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Electron and proton transfer reactions of diiron complexes [Fe2adt(CO)6] (1) and [Fe2adt(CO)4(PMe3)2] (4), with the biomimetic azadithiolate (adt) bridging ligand, have been investigated by real-time IR- and UV-vis-spectroscopic observation to elucidate the role of the adt-N as a potential proton shuttle in catalytic H2 formation. Protonation of the one-electron reduced complex, 1-, occurs on the adt-N yielding 1H and the same species is obtained by one-electron reduction of 1H+. The preference for ligand vs. metal protonation in the Fe2(i,0) state is presumably kinetic but no evidence for tautomerization of 1H to the hydride 1Hy was observed. This shows that the adt ligand does not work as a proton relay in the formation of hydride intermediates in the reduced catalyst. A hydride intermediate 1HHy+ is formed only by protonation of 1H with stronger acid. Adt protonation results in reduction of the catalyst at much less negative potential, but subsequent protonation of the metal centers is not slowed down, as would be expected according to the decrease in basicity. Thus, the adtH+ complex retains a high turnover frequency at the lowered overpotential. Instead of proton shuttling, we propose that this gain in catalytic performance compared to the propyldithiolate analogue might be rationalized in terms of lower reorganization energy for hydride formation with bulk acid upon adt protonation.

Original languageEnglish
Pages (from-to)5582-5588
Number of pages7
JournalChemical Science
Volume10
Issue number21
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Hydrogenase
Protonation
Protons
Metals
Ligands
Hydrides
Carbon Monoxide
Electrons
Catalysts
Acids
Proton transfer
Biomimetics
Alkalinity
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Metal : Vs. ligand protonation and the alleged proton-shuttling role of the azadithiolate ligand in catalytic H2 formation with FeFe hydrogenase model complexes. / Aster, Alexander; Wang, Shihuai; Mirmohades, Mohammad; Esmieu, Charlène; Berggren, Gustav; Hammarström, Leif; Lomoth, Reiner.

In: Chemical Science, Vol. 10, No. 21, 01.01.2019, p. 5582-5588.

Research output: Contribution to journalArticle

Aster, Alexander ; Wang, Shihuai ; Mirmohades, Mohammad ; Esmieu, Charlène ; Berggren, Gustav ; Hammarström, Leif ; Lomoth, Reiner. / Metal : Vs. ligand protonation and the alleged proton-shuttling role of the azadithiolate ligand in catalytic H2 formation with FeFe hydrogenase model complexes. In: Chemical Science. 2019 ; Vol. 10, No. 21. pp. 5582-5588.
@article{893d892fa5ee410eb4ccf37958193ad2,
title = "Metal: Vs. ligand protonation and the alleged proton-shuttling role of the azadithiolate ligand in catalytic H2 formation with FeFe hydrogenase model complexes",
abstract = "Electron and proton transfer reactions of diiron complexes [Fe2adt(CO)6] (1) and [Fe2adt(CO)4(PMe3)2] (4), with the biomimetic azadithiolate (adt) bridging ligand, have been investigated by real-time IR- and UV-vis-spectroscopic observation to elucidate the role of the adt-N as a potential proton shuttle in catalytic H2 formation. Protonation of the one-electron reduced complex, 1-, occurs on the adt-N yielding 1H and the same species is obtained by one-electron reduction of 1H+. The preference for ligand vs. metal protonation in the Fe2(i,0) state is presumably kinetic but no evidence for tautomerization of 1H to the hydride 1Hy was observed. This shows that the adt ligand does not work as a proton relay in the formation of hydride intermediates in the reduced catalyst. A hydride intermediate 1HHy+ is formed only by protonation of 1H with stronger acid. Adt protonation results in reduction of the catalyst at much less negative potential, but subsequent protonation of the metal centers is not slowed down, as would be expected according to the decrease in basicity. Thus, the adtH+ complex retains a high turnover frequency at the lowered overpotential. Instead of proton shuttling, we propose that this gain in catalytic performance compared to the propyldithiolate analogue might be rationalized in terms of lower reorganization energy for hydride formation with bulk acid upon adt protonation.",
author = "Alexander Aster and Shihuai Wang and Mohammad Mirmohades and Charl{\`e}ne Esmieu and Gustav Berggren and Leif Hammarstr{\"o}m and Reiner Lomoth",
year = "2019",
month = "1",
day = "1",
doi = "10.1039/c9sc00876d",
language = "English",
volume = "10",
pages = "5582--5588",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "21",

}

TY - JOUR

T1 - Metal

T2 - Vs. ligand protonation and the alleged proton-shuttling role of the azadithiolate ligand in catalytic H2 formation with FeFe hydrogenase model complexes

AU - Aster, Alexander

AU - Wang, Shihuai

AU - Mirmohades, Mohammad

AU - Esmieu, Charlène

AU - Berggren, Gustav

AU - Hammarström, Leif

AU - Lomoth, Reiner

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Electron and proton transfer reactions of diiron complexes [Fe2adt(CO)6] (1) and [Fe2adt(CO)4(PMe3)2] (4), with the biomimetic azadithiolate (adt) bridging ligand, have been investigated by real-time IR- and UV-vis-spectroscopic observation to elucidate the role of the adt-N as a potential proton shuttle in catalytic H2 formation. Protonation of the one-electron reduced complex, 1-, occurs on the adt-N yielding 1H and the same species is obtained by one-electron reduction of 1H+. The preference for ligand vs. metal protonation in the Fe2(i,0) state is presumably kinetic but no evidence for tautomerization of 1H to the hydride 1Hy was observed. This shows that the adt ligand does not work as a proton relay in the formation of hydride intermediates in the reduced catalyst. A hydride intermediate 1HHy+ is formed only by protonation of 1H with stronger acid. Adt protonation results in reduction of the catalyst at much less negative potential, but subsequent protonation of the metal centers is not slowed down, as would be expected according to the decrease in basicity. Thus, the adtH+ complex retains a high turnover frequency at the lowered overpotential. Instead of proton shuttling, we propose that this gain in catalytic performance compared to the propyldithiolate analogue might be rationalized in terms of lower reorganization energy for hydride formation with bulk acid upon adt protonation.

AB - Electron and proton transfer reactions of diiron complexes [Fe2adt(CO)6] (1) and [Fe2adt(CO)4(PMe3)2] (4), with the biomimetic azadithiolate (adt) bridging ligand, have been investigated by real-time IR- and UV-vis-spectroscopic observation to elucidate the role of the adt-N as a potential proton shuttle in catalytic H2 formation. Protonation of the one-electron reduced complex, 1-, occurs on the adt-N yielding 1H and the same species is obtained by one-electron reduction of 1H+. The preference for ligand vs. metal protonation in the Fe2(i,0) state is presumably kinetic but no evidence for tautomerization of 1H to the hydride 1Hy was observed. This shows that the adt ligand does not work as a proton relay in the formation of hydride intermediates in the reduced catalyst. A hydride intermediate 1HHy+ is formed only by protonation of 1H with stronger acid. Adt protonation results in reduction of the catalyst at much less negative potential, but subsequent protonation of the metal centers is not slowed down, as would be expected according to the decrease in basicity. Thus, the adtH+ complex retains a high turnover frequency at the lowered overpotential. Instead of proton shuttling, we propose that this gain in catalytic performance compared to the propyldithiolate analogue might be rationalized in terms of lower reorganization energy for hydride formation with bulk acid upon adt protonation.

UR - http://www.scopus.com/inward/record.url?scp=85066631508&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85066631508&partnerID=8YFLogxK

U2 - 10.1039/c9sc00876d

DO - 10.1039/c9sc00876d

M3 - Article

AN - SCOPUS:85066631508

VL - 10

SP - 5582

EP - 5588

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 21

ER -