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 language | English |
|---|---|
| Pages (from-to) | 4073-4085 |
| Number of pages | 13 |
| Journal | Inorganic Chemistry |
| Volume | 50 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - May 2 2011 |
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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 journal › Article
}
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
C2 - 21456543
AN - SCOPUS:79955437665
VL - 50
SP - 4073
EP - 4085
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 9
ER -