An unexpected leading role for [Fe2(CO)6(μ-pdt)] in our understanding of [FeFe]-H2ases and the search for clean hydrogen production

Graeme Hogarth

doi:10.1016/j.ccr.2023.215174

An unexpected leading role for [Fe₂(CO)₆(μ-pdt)] in our understanding of [FeFe]-H₂ases and the search for clean hydrogen production

Graeme Hogarth

King's College London

Research output: Contribution to journal › Review article › peer-review

9 Citations (Scopus)

Abstract

When Ziegler and Korav serendipitously prepared [Fe₂(CO)₆(μ-pdt)] in 1979 they could not have anticipated that some 40 years later it would be a mainstay of attempts to understand and replicate the workings of a 4-billion-year-old class of enzyme, [FeFe]-H₂ases, mimicking the function of which has become a major societal goal, namely the clean production of hydrogen. This review traces this journey from chance discovery to innovative exploitation that has brought organometallic chemistry close to the Origins of Life. Much focus is on the extensive substitution chemistry, which can be used to tune both the steric and electronic nature of the diiron centre. This provides access to complexes that are close mimics of the six different identified states of [FeFe]-H₂ases and has allowed chemists and biochemists to piece together a viable overall catalytic cycle. This work has also led to the development of many complexes, including [Fe₂(CO)₆(μ-pdt)] itself, that are (reasonably) efficient proton-reduction catalysts, but finding derivatives that are active for hydrogen oxidation, a key process in a hydrogen fuel cell, remains a significant challenge.

Original language	English
Article number	215174
Journal	COORDINATION CHEMISTRY REVIEWS
Volume	490
Early online date	25 May 2023
DOIs	https://doi.org/10.1016/j.ccr.2023.215174
Publication status	Published - 1 Sept 2023

Keywords

Carbonyl
Catalysis
Cyanide
Dithiolate
Hydrogenase
Substitution

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.ccr.2023.215174

Cite this

@article{6b54bfc317e64382a8f17cc22b0375c8,

title = "An unexpected leading role for [Fe2(CO)6(μ-pdt)] in our understanding of [FeFe]-H2ases and the search for clean hydrogen production",

abstract = "When Ziegler and Korav serendipitously prepared [Fe2(CO)6(μ-pdt)] in 1979 they could not have anticipated that some 40 years later it would be a mainstay of attempts to understand and replicate the workings of a 4-billion-year-old class of enzyme, [FeFe]-H2ases, mimicking the function of which has become a major societal goal, namely the clean production of hydrogen. This review traces this journey from chance discovery to innovative exploitation that has brought organometallic chemistry close to the Origins of Life. Much focus is on the extensive substitution chemistry, which can be used to tune both the steric and electronic nature of the diiron centre. This provides access to complexes that are close mimics of the six different identified states of [FeFe]-H2ases and has allowed chemists and biochemists to piece together a viable overall catalytic cycle. This work has also led to the development of many complexes, including [Fe2(CO)6(μ-pdt)] itself, that are (reasonably) efficient proton-reduction catalysts, but finding derivatives that are active for hydrogen oxidation, a key process in a hydrogen fuel cell, remains a significant challenge.",

keywords = "Carbonyl, Catalysis, Cyanide, Dithiolate, Hydrogenase, Substitution",

author = "Graeme Hogarth",

note = "Funding Information: I would like to thank the many talented and hard-working people who have worked on [FeFe]-H2ase biomimics in my labs at both University College London and King's College London and collaborators across the globe including Katherine Holt (UCL), Ebbe Nordlander (Lund University, Sweden), Shariff Kabir and Shishir Ghosh (Jahangirnager University, Bangladesh), Michael Richmond (University of North Texas, USA) and Frantisek Hartl (Reading), together with various funding agencies for supporting this work. Our initial efforts in this area came out of one unfortunate and one fortunate event. The former was a twice ruptured Achilles tendon (squash) in 2004 that left me in plaster for ca. 9 months and meant that I had time to read about the early work in this area and write a review of diiron chemistry [361]. The fortune was that on return to UCL, my (then) colleague Andrea Sella had prepared a sample of 1 to do some NMR studies (with the late Sean McGrady) and it was seeing this sample in our shared fridge that prompted me (with two high school students on a Nuffield Summer placement) to carry out our first reaction of 1 with dppm in 2005. Publisher Copyright: {\textcopyright} 2023 The Author",

year = "2023",

month = sep,

day = "1",

doi = "10.1016/j.ccr.2023.215174",

language = "English",

volume = "490",

journal = "COORDINATION CHEMISTRY REVIEWS",

issn = "0010-8545",

publisher = "Elsevier",

}

TY - JOUR

T1 - An unexpected leading role for [Fe2(CO)6(μ-pdt)] in our understanding of [FeFe]-H2ases and the search for clean hydrogen production

AU - Hogarth, Graeme

N1 - Funding Information: I would like to thank the many talented and hard-working people who have worked on [FeFe]-H2ase biomimics in my labs at both University College London and King's College London and collaborators across the globe including Katherine Holt (UCL), Ebbe Nordlander (Lund University, Sweden), Shariff Kabir and Shishir Ghosh (Jahangirnager University, Bangladesh), Michael Richmond (University of North Texas, USA) and Frantisek Hartl (Reading), together with various funding agencies for supporting this work. Our initial efforts in this area came out of one unfortunate and one fortunate event. The former was a twice ruptured Achilles tendon (squash) in 2004 that left me in plaster for ca. 9 months and meant that I had time to read about the early work in this area and write a review of diiron chemistry [361]. The fortune was that on return to UCL, my (then) colleague Andrea Sella had prepared a sample of 1 to do some NMR studies (with the late Sean McGrady) and it was seeing this sample in our shared fridge that prompted me (with two high school students on a Nuffield Summer placement) to carry out our first reaction of 1 with dppm in 2005. Publisher Copyright: © 2023 The Author

PY - 2023/9/1

Y1 - 2023/9/1

N2 - When Ziegler and Korav serendipitously prepared [Fe2(CO)6(μ-pdt)] in 1979 they could not have anticipated that some 40 years later it would be a mainstay of attempts to understand and replicate the workings of a 4-billion-year-old class of enzyme, [FeFe]-H2ases, mimicking the function of which has become a major societal goal, namely the clean production of hydrogen. This review traces this journey from chance discovery to innovative exploitation that has brought organometallic chemistry close to the Origins of Life. Much focus is on the extensive substitution chemistry, which can be used to tune both the steric and electronic nature of the diiron centre. This provides access to complexes that are close mimics of the six different identified states of [FeFe]-H2ases and has allowed chemists and biochemists to piece together a viable overall catalytic cycle. This work has also led to the development of many complexes, including [Fe2(CO)6(μ-pdt)] itself, that are (reasonably) efficient proton-reduction catalysts, but finding derivatives that are active for hydrogen oxidation, a key process in a hydrogen fuel cell, remains a significant challenge.

AB - When Ziegler and Korav serendipitously prepared [Fe2(CO)6(μ-pdt)] in 1979 they could not have anticipated that some 40 years later it would be a mainstay of attempts to understand and replicate the workings of a 4-billion-year-old class of enzyme, [FeFe]-H2ases, mimicking the function of which has become a major societal goal, namely the clean production of hydrogen. This review traces this journey from chance discovery to innovative exploitation that has brought organometallic chemistry close to the Origins of Life. Much focus is on the extensive substitution chemistry, which can be used to tune both the steric and electronic nature of the diiron centre. This provides access to complexes that are close mimics of the six different identified states of [FeFe]-H2ases and has allowed chemists and biochemists to piece together a viable overall catalytic cycle. This work has also led to the development of many complexes, including [Fe2(CO)6(μ-pdt)] itself, that are (reasonably) efficient proton-reduction catalysts, but finding derivatives that are active for hydrogen oxidation, a key process in a hydrogen fuel cell, remains a significant challenge.

KW - Carbonyl

KW - Catalysis

KW - Cyanide

KW - Dithiolate

KW - Hydrogenase

KW - Substitution

UR - http://www.scopus.com/inward/record.url?scp=85160394077&partnerID=8YFLogxK

U2 - 10.1016/j.ccr.2023.215174

DO - 10.1016/j.ccr.2023.215174

M3 - Review article

AN - SCOPUS:85160394077

SN - 0010-8545

VL - 490

JO - COORDINATION CHEMISTRY REVIEWS

JF - COORDINATION CHEMISTRY REVIEWS

M1 - 215174

ER -