Book of abstracts version 5

Synthesis of a ligand for a synthetic [NiFe] hydrogenase model
Figure 1 : Overall reaction
Author
Egor Silin
Academy of Technology for Health and Environment
Avans Hogeschool, Breda
University of Leiden
ligand for a synthetic [NiFe] hydrogenase model
Abstract
Hydrogen gas is a good candidate to replace the fossil fuels as an energy carrier. The hydrogen economy relies on the
vision to replace the fossil fuels, using hydrogen as a low-carbon energy source. A way of producing hydrogen gas is using
a hydrogen evolution reaction with an electro catalyst. This is possible with an enzyme present in certain microorganisms
and is called hydrogenase [1]. The goal of this study is to synthesize a ligand with all substituted carbons present in the
benzene, which can be used for the synthesis of the hydrogenase model for the University of Leiden. The ligand must
have a complex of four sulphur atoms, so it could donate electrons to the metal complex present in the hydrogenase
model. This is shown in Figure 1. Currently the ligand is being synthesized using Hexakis(bromomethyl)benzene as starting
material. First, the present bromides were replaced with thioureum groups and hydrolysed with a base, to create a
thiolproduct. After the synthesis of the thiolproduct, the product has reacted with 1 -chloro-2-methyl-2-propanol,
resulting a bridge where another sulphur atom can be attached. The next step was to replace the hydroxy group with a
halogen, using the thionylchloride as reagent. This reaction gave a shift of the two present methyl -groups to the beta
carbon[3]. At last, the product from the previous step has reacted with thioureum under nitrogen, resulting the final
ligand product. This is shown in Figure 2. The monsters were analysed with FTIR and 1 H-NMR.
Keywords: Hydrogenas e, metal-ligand, Sn 2 -reaction.
Table of content
Figure 1: Target molecule
Figure 2: Reaction equation
[1] Lubitz, W., Ogata, H., Rüdiger, O., & Reijerse, E. (2014). Hydrogenases. Chemical Reviews , 4081-4148.
[2] ] Verhagen, J. A., Ellis, D. D., Lutz, M., Spek, A. L., & Bouwman, E. (2002). Synthesis, characterisation and crystal
structures of new nickel complexes in S4 coordination spheres; an unprecedented rearrangement during ligand synthesis.
The Royal Society of Chemistry , 1275-1280.
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