Simple ligand effects switch a hydrogenase mimic between H 2 and O 2 activation

Kyoungmok Kim, Takahiro Matsumoto, Andrew Robertson, Hidetaka Nakai, Seiji Ogo

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)1394-1400
Number of pages7
JournalChemistry - An Asian Journal
Volume7
Issue number6
DOIs
Publication statusPublished - Jun 1 2012

Fingerprint

Hydrogenase
Biomimetics
Chemical activation
Switches
Ligands
Photoelectron Spectroscopy
Oxygenation
X ray analysis
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Mass Spectrometry
Magnetic Resonance Spectroscopy
X ray photoelectron spectroscopy
X-Rays
Electrons
nickel-iron hydrogenase
sodium borohydride
hexamethylbenzene
hydroquinone
Proton Magnetic Resonance Spectroscopy

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Simple ligand effects switch a hydrogenase mimic between H 2 and O 2 activation. / Kim, Kyoungmok; Matsumoto, Takahiro; Robertson, Andrew; Nakai, Hidetaka; Ogo, Seiji.

In: Chemistry - An Asian Journal, Vol. 7, No. 6, 01.06.2012, p. 1394-1400.

Research output: Contribution to journalArticle

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