Novel reactions of homodinuclear Ni2 complexes [Ni(RNPyS4)]2 with Fe3(CO)12 to give heterotrinuclear NiFe2 and mononuclear Fe complexes relevant to [NiFe]- and [Fe]-hydrogenases. Issue 15 (6th March 2015)

• Record Type: Journal Article
• Authors: Song, Li-Cheng; Cao, Meng; Wang, Yong-Xiang
• Is Part Of: Dalton transactions. Volume 44:Issue 15(2015)
• Page Start: 6797
• Page End: 6808
• Publication Date: 2015-03-06
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt00067j
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The [RNPy S4 ]-type ligand-containing [NiFe]- and [Fe]-hydrogenase model complexes NiFe2 (RNPy S4 )(CO)5 (2a–2e ) and Fe(RNPy S4 )(CO) (3a–3e ) have been prepared and found to be catalysts for proton reduction to H2 . Abstract : The homodinuclear complexes [Ni(RNPy S4 )]2 (1a–1e ; RNPy S4 = 2, 6-bis(2-mercaptophenylthiomethyl)-4- R -pyridine; R = H, MeO, Cl, Br, i-Pr) were found to be prepared by reactions of the in situ generated Li2 [Ni(1, 2-S2 C6 H4 )2 ] with 2, 6-bis[(tosyloxy)methyl]pyridine and its substituted derivatives 2, 6-bis[(tosyloxy)methyl]-4- R -pyridine. Further reactions of1a–1e with Fe3 (CO)12 gave both heterotrinuclear complexes NiFe2 (RNPy S4 )(CO)5 (2a–2e ) and mononuclear complexes Fe(RNPy S4 )(CO) (3a–3e ), unexpectedly. Interestingly, complexes2a–2e and3a–3e could be regarded as models for the active sites of [NiFe]- and [Fe]-hydrogenases, respectively. All the prepared complexes were characterized by elemental analysis, spectroscopy, and particularly for some of them, by X-ray crystallography. In addition, the electrochemical properties of2a–2e and3a–3e as well as the electrocatalytic H2 production catalyzed by2a–2e and3a–3e were investigated by CV techniques.