Incorporating peptides in the outer-coordination sphere of bioinspired electrocatalysts for hydrogen production

Avijita Jain, Sheri Lense, John Linehan, Simone Raugei, Herman Cho, Daniel L DuBois, Wendy J. Shaw

Research output: Contribution to journalArticle

55 Citations (Scopus)

Abstract

Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(PPh 2NR 2)2]2+ complexes in which R is a mono- or dipeptide. These complexes represent a first step in the development of an outer-coordination sphere for this class of complexes that can mimic the outer-coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni(PPh 2NPh 2)2] 2+ complex in an acetonitrile solution with turnover frequencies for hydrogen production ranging from 14 to 25 s-1 in the presence of p-cyanoanilinium trifluoromethanesulfonate and from 135 to 1000 s-1 in the presence of protonated dimethylformamide, with moderately low overpotentials, ∼0.3 V. The addition of small amounts of water results in rate increases of 2-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(PR 2NR′ 2) 2]2+ molecular catalytic core to begin to mimic the multifunctional outer-coordination sphere of enzymes.

Original languageEnglish
Pages (from-to)4073-4085
Number of pages13
JournalInorganic Chemistry
Volume50
Issue number9
DOIs
Publication statusPublished - May 2 2011

Fingerprint

electrocatalysts
Electrocatalysts
hydrogen production
Hydrogen production
peptides
Peptides
enzymes
Hydrogenase
Dimethylformamide
dynamic structural analysis
Dipeptides
Structural dynamics
Enzymes
acetonitrile
Ligands
ligands
Water
water

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Incorporating peptides in the outer-coordination sphere of bioinspired electrocatalysts for hydrogen production. / Jain, Avijita; Lense, Sheri; Linehan, John; Raugei, Simone; Cho, Herman; DuBois, Daniel L; Shaw, Wendy J.

In: Inorganic Chemistry, Vol. 50, No. 9, 02.05.2011, p. 4073-4085.

Research output: Contribution to journalArticle

@article{35f8cab604a9407bab53b49aa0287ae6,
title = "Incorporating peptides in the outer-coordination sphere of bioinspired electrocatalysts for hydrogen production",
abstract = "Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(PPh 2NR 2)2]2+ complexes in which R is a mono- or dipeptide. These complexes represent a first step in the development of an outer-coordination sphere for this class of complexes that can mimic the outer-coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni(PPh 2NPh 2)2] 2+ complex in an acetonitrile solution with turnover frequencies for hydrogen production ranging from 14 to 25 s-1 in the presence of p-cyanoanilinium trifluoromethanesulfonate and from 135 to 1000 s-1 in the presence of protonated dimethylformamide, with moderately low overpotentials, ∼0.3 V. The addition of small amounts of water results in rate increases of 2-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(PR 2NR′ 2) 2]2+ molecular catalytic core to begin to mimic the multifunctional outer-coordination sphere of enzymes.",
author = "Avijita Jain and Sheri Lense and John Linehan and Simone Raugei and Herman Cho and DuBois, {Daniel L} and Shaw, {Wendy J.}",
year = "2011",
month = "5",
day = "2",
doi = "10.1021/ic1025872",
language = "English",
volume = "50",
pages = "4073--4085",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Incorporating peptides in the outer-coordination sphere of bioinspired electrocatalysts for hydrogen production

AU - Jain, Avijita

AU - Lense, Sheri

AU - Linehan, John

AU - Raugei, Simone

AU - Cho, Herman

AU - DuBois, Daniel L

AU - Shaw, Wendy J.

PY - 2011/5/2

Y1 - 2011/5/2

N2 - Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(PPh 2NR 2)2]2+ complexes in which R is a mono- or dipeptide. These complexes represent a first step in the development of an outer-coordination sphere for this class of complexes that can mimic the outer-coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni(PPh 2NPh 2)2] 2+ complex in an acetonitrile solution with turnover frequencies for hydrogen production ranging from 14 to 25 s-1 in the presence of p-cyanoanilinium trifluoromethanesulfonate and from 135 to 1000 s-1 in the presence of protonated dimethylformamide, with moderately low overpotentials, ∼0.3 V. The addition of small amounts of water results in rate increases of 2-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(PR 2NR′ 2) 2]2+ molecular catalytic core to begin to mimic the multifunctional outer-coordination sphere of enzymes.

AB - Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(PPh 2NR 2)2]2+ complexes in which R is a mono- or dipeptide. These complexes represent a first step in the development of an outer-coordination sphere for this class of complexes that can mimic the outer-coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni(PPh 2NPh 2)2] 2+ complex in an acetonitrile solution with turnover frequencies for hydrogen production ranging from 14 to 25 s-1 in the presence of p-cyanoanilinium trifluoromethanesulfonate and from 135 to 1000 s-1 in the presence of protonated dimethylformamide, with moderately low overpotentials, ∼0.3 V. The addition of small amounts of water results in rate increases of 2-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(PR 2NR′ 2) 2]2+ molecular catalytic core to begin to mimic the multifunctional outer-coordination sphere of enzymes.

UR - http://www.scopus.com/inward/record.url?scp=79955437665&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79955437665&partnerID=8YFLogxK

U2 - 10.1021/ic1025872

DO - 10.1021/ic1025872

M3 - Article

VL - 50

SP - 4073

EP - 4085

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 9

ER -