Research Internship

Michael Rotter Address: Fritz-Haber-Weg 6

(M. Sc., PhD student) 76131 Karlsruhe, Germany
Group of Prof. Dr. Stefan Bräse Phone: +49 721 608-46597
Karlsruhe Institute of Technology (KIT) E-mail: michael.rotter@kit.edu
Institute of Organic Chemistry Web: https://www.ioc.kit.edu/braese/index.php

Porphyrin Transition Metal Complexes for CO2 Reduction

The molecular class of porphyrins combines a universal ligand system with versatile functionality,
providing all the requirements for synthesizing novel multimetallic centers. Complex biological
systems such as the Fe(II)-Ni(II) center of the carbon monoxide dehydrogenase, enabling CO2
reduction under physiological conditions, can consequently be recreated and investigated in a
simplified form. This makes a valuable contribution towards a better understanding of biological
models to apply cooperative metal-metal interaction in catalysis in the future.
The ability of metalloporphyrins to catalyze chemical reactions of small molecules can be exploited for
reductions. In particular, the electrochemical reduction of CO2 to valuable carbon sources catalyzed
by porphyrin-metal complexes has experienced ever-increasing attention since the end of the last
century. CO2 is a thermodynamically stable molecule whose reduction to a radical anion (CO2 / CO2•–)
with a potential of –2.2 V vs. the SCE (saturated calomel electrode) can only be achieved in an
endergonic way. Many homogenous and heterogenous catalysts mostly in non-aqueous solutions
have been developed and evaluated to overcome efficiently this highly uphill conversion, including
precious metals like Re, Ru, Ir, Au and non-precious metals like Fe, Ni, Co and Mn.

Figure 1: Carobon monoxide dehydrogenase as natures example (left) with the reactive nickel (orange) and iron (red) center[1];
Mimicrated artifical bimetallic reaction center as laboratories example (right) with iron (red) – porphyrin center[2].

To investigate various oxidation states of transition metals, three different porphyrin-monomers will
be examined.

[1] Dobbek et al., Science 2001, 293, 1281-1285. [2] Naruta et al., Chem. Mater. 2017, 29, 7140-
7150.
The first one is the conventional tetraphenyl-porphyrin, which is
capable of coordinating transition metals of the oxidation state +2
in their center. Secondly, the so-called N-confused-porphyrin will
be studied. This porphyrin-monomer will most likely coordinate the
oxidation state +3 due to their additional carbon at the porphyrins
inner site. Still missing is the oxidation state +1, which can be
introduced through the N-fused-porphyrin. With these porphyrin
monomers, a wide range of transition metals in different oxidation
states can be covered. The next step is to functionalize these
scaffolds in an A3B manor to build porphyrin dimers and investigate
metal to metal interactions of transition metals in different
Figure 2: Molecular structure of the
distances to each other. porphyrin monomers of choice.
Two of the target molecules were successfully
synthesized over the last years. The aim of this
work is to re-synthesize these ligands and attach
them with different transition metals of interest.
These complexes will be studied for their potential
to reduce CO2 via cyclovoltammetry. Other studies
like Mössbauer spectroscopy of iron complexes will
be also elaborated. Furthermore, by finding a
strategy to synthesize the N-confused-dimer, a
completely new porphyrin ligand can be built,
Figure 3: Synthesized Figure 4: Synthesized porphyrin
porphyrin dimer which can
open up novel investigations of metal dimer which can investigate metal
investigate metal interactions. The distance variation will be interactions of the oxidation state
interactions of the applied through different linker positions. In +1 and +2.
oxidation state +2. this case, a phenyl-linker was chosen which
can hold two porphyrins in ortho-, meta- or para-position.
You will work in the research group of Prof. Bräse at campus south, which accounts more than 30
people from all around the world working on their PhD, Master thesis or PostDoc. The official language
in our seminars and meetings is English. The group is divided in subgroups depending on their research
topic. Besides to our lab environment our group also likes to gather around for activities like BBQs,
climbing or playing beach volleyball. The university is in the centre of Karlsruhe surrounded by a
spacious garden and a neighbouring forest. Karlsruhe is in the south west of Germany and offers
excellent connections to explore not only Germany, but also international cities and places such as
Paris, Brussels, Amsterdam or maybe the alps in Austria or Switzerland.

Figure 5: Our group after winning 2nd place of the faculty tournament (left); Castle and city of Karlsruhe at night (right).