TY - JOUR
T1 - Simple ligand effects switch a hydrogenase mimic between H 2 and O 2 activation
AU - Kim, Kyoungmok
AU - Matsumoto, Takahiro
AU - Robertson, Andrew
AU - Nakai, Hidetaka
AU - Ogo, Seiji
N1 - Copyright:
Copyright 2012 Elsevier B.V., All rights reserved.
PY - 2012/6
Y1 - 2012/6
N2 - Herein, we report a [NiRu] biomimetic system for O 2-tolerant [NiFe]hydrogenases and demonstrate that electron donation to the [NiRu] center can switch the system between the activation of H 2 and O 2 through simple ligand effects by using hexamethylbenzene and pentamethylcyclopentadienyl ligands, respectively. Furthermore, we present the synthesis and direct observations of a [NiRu]-peroxo species, which was formed by the oxygenation of a Ni-SIa model [NiRu] complex, that we propose as a biomimetic analogue of O 2-bound species (OBS) of O 2-tolerant [NiFe]hydrogenases. The [NiRu]-peroxo complex was fully characterized by X-ray analysis, X-ray photoelectron spectroscopy (XPS), mass spectrometry, and 1H NMR spectroscopy. The OBS analogue was capable of oxidizing p-hydroquinone and sodium borohydride to turn back into the Ni-SIa model complex.
AB - Herein, we report a [NiRu] biomimetic system for O 2-tolerant [NiFe]hydrogenases and demonstrate that electron donation to the [NiRu] center can switch the system between the activation of H 2 and O 2 through simple ligand effects by using hexamethylbenzene and pentamethylcyclopentadienyl ligands, respectively. Furthermore, we present the synthesis and direct observations of a [NiRu]-peroxo species, which was formed by the oxygenation of a Ni-SIa model [NiRu] complex, that we propose as a biomimetic analogue of O 2-bound species (OBS) of O 2-tolerant [NiFe]hydrogenases. The [NiRu]-peroxo complex was fully characterized by X-ray analysis, X-ray photoelectron spectroscopy (XPS), mass spectrometry, and 1H NMR spectroscopy. The OBS analogue was capable of oxidizing p-hydroquinone and sodium borohydride to turn back into the Ni-SIa model complex.
UR - http://www.scopus.com/inward/record.url?scp=84861563005&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84861563005&partnerID=8YFLogxK
U2 - 10.1002/asia.201101020
DO - 10.1002/asia.201101020
M3 - Article
C2 - 22383335
AN - SCOPUS:84861563005
VL - 7
SP - 1394
EP - 1400
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
SN - 1861-4728
IS - 6
ER -