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A Nickel(II)–Sulfur‐Based Radical‐Ligand Complex as a Functional Model of Hydrogenase
Author(s) -
Begum Ameerunisha,
Moula Golam,
Sarkar Sabyasachi
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001812
Subject(s) - hydrogenase , nickel , electron paramagnetic resonance , sulfur , chemistry , ligand (biochemistry) , aqueous solution , reduction (mathematics) , electrochemistry , hydrogen , crystallography , inorganic chemistry , nuclear magnetic resonance , biochemistry , organic chemistry , mathematics , physics , receptor , geometry , electrode
Better than nature! A nickel(II) dithiolene complex [Ni II (L 2− )(L −. )][PPh 4 ] ( 1 ; see figure; L=1,2‐dicarbomethoxyethylene dithiolate) electrocatalyzes hydrogen evolution at the lowest achievable reduction potential ( ${{{\rm E}{{{\rm {\rm red}}\hfill \atop {\rm {\rm p}}\hfill}}}}$ , −0.69 V) in CH 3 CN and also in aqueous medium ( ${{{\rm E}{{{\rm {\rm red}}\hfill \atop {\rm {\rm p}}\hfill}}}}$ , −0.71 V) to date. Compound 1 shows strikingly similar EPR and reduction potential values to those observed with native Ni‐containing hydrogenases.