Proton affinity studies of nickel N2S2 complexes and control of aggregation

  • Nicholas A. Arnet
  • Nattamai Bhuvanesh
  • Marcetta Y. DarensbourgEmail author
Original Paper
Part of the following topical collections:
  1. Joan Broderick: Papers in Celebration of Her 2019 ACS Alfred Bader Award in Bioinorganic or Bioorganic Chemistry


The thiolate ligands of [NiFe]-H2ase enzymes have been implicated as proton-binding sites for the reduction/oxidation of H+/H2. This study examines the ligand effect on reactivity of NiN2S2 complexes with an array of acids in methanol solution. UV–Vis absorption spectroscopy is utilized to observe the transformation from the monomeric species to a trimetallic complex that is formed after proton-induced ligand dissociation. Nickel complexes with a flexible (propyl and ethyl) N to N linker were found to readily form the trimetallic complex with acids as weak as ammonium (pKa = 10.9 in methanol). A more constrained nickel complex with a diazacycloheptane N to N linker required stronger acids such as 2,2-dichloroacetic acid (pKa = 6.38 in methanol) to form the trimetallic complex and featured the formation of an NiN2S2H+ complex with acetic acid (pKa = 9.63 in methanol). The most strained ligand, which featured a diazacyclohexane backbone, readily dissociated from the nickel center upon mixture with acids with pKa ≤ 9.63 and showed no evidence of a trimetallic species with any acid. This research highlights the dramatic differences in reactivity with proton sources that can be imparted by minor alterations to ligand geometry and strain.

Graphical abstract


Hydrogenase Pendant base Clothespin effect 



This manuscript is submitted in recognition and appreciation of the bioinorganic research of Joan Broderick that has so greatly advanced understanding of the critical roles of iron-sulfur chemistry within biosynthetic pathways. Our work was funded by the National Science Foundation (CHE-1665258) and the Robert A. Welch Foundation (A-0924).

Compliance with ethical standards

Conflict of interest

The authors declare no conflict of interest.

Data availability

The crystallographic data for complex were deposited in the Cambridge Crystallographic Data Centre with a CDC number 1917616.

Supplementary material

775_2019_1671_MOESM1_ESM.pdf (2.4 mb)
Experimental procedures; additional spectroscopic and electrochemical data; Crystallographic data for complex [12Ni3]2+ (CIF) (pdf 2421 kb)


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Copyright information

© Society for Biological Inorganic Chemistry (SBIC) 2019

Authors and Affiliations

  • Nicholas A. Arnet
    • 1
  • Nattamai Bhuvanesh
    • 1
  • Marcetta Y. Darensbourg
    • 1
    Email author
  1. 1.Department of ChemistryTexas A&M UniversityCollege StationUSA

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