Jump to main content
Jump to site search

Issue 22, 2016
Previous Article Next Article

Why is a proton transformed into a hydride by [NiFe] hydrogenases? An intrinsic reactivity analysis based on conceptual DFT

Author affiliations

Abstract

The hydrogen evolution reaction (HER) catalysed by [NiFe] hydrogenases entails a series of chemical events involving great mechanistic interest. In an attempt to understand and delve into the question about ‘Why does nature work in that way?’, an in-depth intrinsic reactivity analysis based on conceptual DFT has been carried out focusing on the so-called I1 to Ni-C step, i.e. our work tries to answer how and why the proton attached to the reactive sulphur atom from one of the exo-cyclic cysteine residues is transformed into a bridging hydride to be shared between the Ni/Fe metals in the active site of [NiFe] hydrogenases, which involves not only H migration, but also a change of the charge state on Ni from Ni(I) to Ni(III). Our DFT results suggest that the transformation is motivated by spontaneous rearrangements of the electron density, and stabilisation comes from the decrease of both electronic activity and electrophilicity index from Ni.

Graphical abstract: Why is a proton transformed into a hydride by [NiFe] hydrogenases? An intrinsic reactivity analysis based on conceptual DFT

Back to tab navigation

Supplementary files

Article information


Submitted
11 Feb 2016
Accepted
10 May 2016
First published
11 May 2016

Phys. Chem. Chem. Phys., 2016,18, 15369-15374
Article type
Paper

Why is a proton transformed into a hydride by [NiFe] hydrogenases? An intrinsic reactivity analysis based on conceptual DFT

S. Qiu, L. M. Azofra, D. R. MacFarlane and C. Sun, Phys. Chem. Chem. Phys., 2016, 18, 15369
DOI: 10.1039/C6CP00948D

Social activity

Search articles by author

Spotlight

Advertisements