Mononuclear nickel(III) and nickel(II) thiolate complexes with intramolecular S-H proton interacting with both sulfur and nickel: relevance to the [NiFe]/[NiFeSe] hydrogenases

Journal of the American Chemical Society
Chien-Ming LeeWen-Feng Liaw

Abstract

Mononuclear, distorted square planar [Ni(II)(ER)(P(o-C(6)H(4)S)(2)(o-C(6)H(4)SH))](-) (ER = SePh (1), 2-S-C(4)H(3)S (2)) with a S-H proton directly interacting with both nickel and sulfur atoms were prepared by reaction of [Ni(CO)(SePh)(3)](-)/[Ni(CO)(2-S-C(4)H(3)S)(3)](-) and P(o-C(6)H(4)SH)(3), individually. The presence of combinations of intramolecular [Ni-S...H-SR]/[Ni...H-SR] interactions was verified in the solid state by the observation of an IR nu(SH) stretching band (2273 and 2283 cm(-)(1) (KBr) for complexes 1 and 2, individually) and (1)H NMR spectra (delta 8.079 (d) (CD(2)Cl(2)) and 8.39 (d) (C(4)D(8)O) ppm (-SH) for complexes 1 and 2, respectively) and subsequently confirmed by X-ray diffraction study. The exo-thiol proton (o-C(6)H(4)SH) in complexes 1 and 2 was identified as a D(2)O exchangeable proton from NMR and IR studies and was quantitatively removed by Lewis base Et(3)N to yield Ni(II) dimer [Ni(II)(P(o-C(6)H(4)S)(3))](2)(2)(-) (5). Instead of the ligand-based oxidation to form dinuclear Ni(II) complexes and dichalcogenide, oxidation of THF-CH(3)CN solution of complexes 1 and 2 by O(2) resulted in the formation of the mononuclear, distorted trigonal bipyramidal [Ni(III)(ER)(P(o-C(6)H(4)S)(3))](-) (ER = SeP...Continue Reading

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Citations

Nov 10, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Hao-Ching ChangWay-Zen Lee
Dec 25, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Claire Wombwell, Erwin Reisner
Feb 16, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Hao-Ching ChangWay-Zen Lee
Nov 26, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Atanu BanerjeeKajal Krishna Rajak
Jun 22, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Li-Cheng SongHai-Bin Song
Jun 1, 2016·Chemical Science·Tzung-Wen ChiouWen-Feng Liaw
Jun 24, 2010·Journal of the American Chemical Society·Chien-Ming LeeGene-Hsiang Lee
Dec 1, 2012·Journal of the American Chemical Society·Katharina WeberWolfgang Lubitz
Nov 5, 2019·Inorganic Chemistry·Chase S Richburg, Byron H Farnum
Jan 7, 2015·Journal of the American Chemical Society·Lu GanAnne K Jones
Apr 14, 2020·Journal of the American Chemical Society·Chuan-Kuei ChiangChien-Ming Lee
Jan 7, 2021·Inorganic Chemistry·Ayan DasAmit Majumdar

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