Top Organomet Chem (2016) 59: 233–272
DOI: 10.1007/3418_2015_146
# Springer International Publishing Switzerland 2015
Published online: 16 September 2015
Biomimetic Complexes for Production
of Dihydrogen and Reduction of CO 2
Lu Gan, David Jennings, Joseph Laureanti, and Anne Katherine Jones
Abstract The active sites of several bioenergetically important metalloenzymes
that perform multielectron redox reactions feature heterobimetallic complexes.
Herein, we review recent understanding of the structure and mechanisms of
hydrogenases, formate dehydrogenases, and carbon monoxide dehydrogenases.
Then we evaluate progress toward creating functional, small-molecule complexes
that reproduce the activities of these active sites. Particular emphasis is placed on
comparing catalytic properties including turnover number, turnover frequency,
required overpotential, and catalyst stability. Opportunities and challenges for
future work are also considered.
Keywords Bio-inspired metallocomplexes • Biomimicry • Carbon monoxide
dehydrogenase • Catalysis • Energy • Formate dehydrogenase • Hydrogenase
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
2 Biological Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.1 Hydrogenases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.2 Carbon Monoxide Dehydrogenases (CODHs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
2.3 Formate Dehydrogenase (FDH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3 Hydrogen Production Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
3.1 Bimetallic Hydrogen Production Electrocatalysts Featuring Nickel . . . . . . . . . . . . . . . . 244
3.2 Bimetallic Hydrogen Production Electrocatalysts Featuring Only Iron . . . . . . . . . . . . 245
3.3 Monometallic Proton Reduction Electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
L. Gan, D. Jennings, J. Laureanti, and A.K. Jones (*)
Department of Chemistry and Biochemistry, Arizona State University, Tempe,
AZ 85287, USA
e-mail: jonesak@asu.edu
DOI: 10.1007/3418_2015_146
# Springer International Publishing Switzerland 2015
Published online: 16 September 2015
Biomimetic Complexes for Production
of Dihydrogen and Reduction of CO 2
Lu Gan, David Jennings, Joseph Laureanti, and Anne Katherine Jones
Abstract The active sites of several bioenergetically important metalloenzymes
that perform multielectron redox reactions feature heterobimetallic complexes.
Herein, we review recent understanding of the structure and mechanisms of
hydrogenases, formate dehydrogenases, and carbon monoxide dehydrogenases.
Then we evaluate progress toward creating functional, small-molecule complexes
that reproduce the activities of these active sites. Particular emphasis is placed on
comparing catalytic properties including turnover number, turnover frequency,
required overpotential, and catalyst stability. Opportunities and challenges for
future work are also considered.
Keywords Bio-inspired metallocomplexes • Biomimicry • Carbon monoxide
dehydrogenase • Catalysis • Energy • Formate dehydrogenase • Hydrogenase
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
2 Biological Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.1 Hydrogenases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.2 Carbon Monoxide Dehydrogenases (CODHs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
2.3 Formate Dehydrogenase (FDH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3 Hydrogen Production Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
3.1 Bimetallic Hydrogen Production Electrocatalysts Featuring Nickel . . . . . . . . . . . . . . . . 244
3.2 Bimetallic Hydrogen Production Electrocatalysts Featuring Only Iron . . . . . . . . . . . . 245
3.3 Monometallic Proton Reduction Electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
L. Gan, D. Jennings, J. Laureanti, and A.K. Jones (*)
Department of Chemistry and Biochemistry, Arizona State University, Tempe,
AZ 85287, USA
e-mail: jonesak@asu.edu