The_Catalyst_Review_December_2023 - 3

Industry Perspective
The views expressed are those of the individual author and may not reflect those of The Catalyst Review or TCGR.
The Ethenolysis Edge
A Novel Application of Ruthenium Produces
Game-changing, Highly Efficient Catalysts
By Rafał Gawin
In an industrial landscape increasingly defined by its environmental footprint, a team of Apeiron Synthesis has made a landmark breakthrough:
They have developed a highly efficient catalyst for ethenolysis. Rafał Gawin, Andrzej Tracz, Michał Chwalba, Anna Kozakiewicz, Bartosz
Trzaskowski, and Krzysztof Skowerski have recently published their work in The Journal of Amercian Chemical Society. The development of
ruthenium-based catalysts for ethenolysis - a reaction that could improve the chances in the fight against reliance on non-renewable resources-
signals an industrial milestone and a step toward greener chemistry.
Stability Meets Efficiency
The synthesis of Apeiron's novel catalyst, commercially known as Slashcat, has been marked by years of experience in olefin metathesis
development and consultations. The spirocyclic alkyl amino carbenes (CAACs) are at the core of their structure, a molecular architecture that
confers unprecedented stability and efficiency. The ethenolysis of methyl oleate was conducted using an exceptionally low catalyst concentration
of 100 parts per billion. This resulted in an impressive turnover number (TON) reaching 2.6 million, a figure substantially surpassing prior records,
in which the following were achieved:
* a TON of 340,000 at 1 part per million; and
* a TON of 744,000 at 0.5 parts per million catalyst (for phenyl-substituted complexes) concentration.
The outcomes of this conversion, namely 1-decene and
methyl 9-decenoate (9-DAME), serve as commercially
important starting materials for a host of various chemicals
used for manufacturing fuels, surfactants, lubricants, waxes,
and compounds used in insect attractants.
The team has proven that the ethenolysis reaction can be
efficiently conducted using this new catalyst with sunflower
and rapeseed oils methyl esters. This was accomplished with
a minimal catalyst concentration of 0.5 parts per million,
achieving an impressive TON up to 964,000.
Sunflower and rapeseed are common, renewable, and
sustainable crops, positioning this process as a green solution
for industries that struggle to gain independence from nonreliable
resources. The implications are vast - such as ability
to convert these oils into various chemicals that form the core
of many industries, from polymers to energy.
Why It Matters
The resilience of these compounds toward bimolecular
decomposition - a common challenge in catalyst design
- directly correlates with their performance, ensuring high
turnover numbers and long catalyst lifetimes. The spirocyclic
motif in the CAACs reduces bulkiness, creating more
space around the ruthenium atom. This facilitates substrate
accommodation, enhancing the reaction's efficiency - a
masterstroke of molecular design.
This research holds implications for the industrial sector
in regard to sustainability and roadmap towards green
chemistry. It showcases a way to use less to achieve more,
substantially lowering the amount of catalyst needed for
chemical processes. This efficiency, coupled with using
renewable feedstocks, represents a significant step towards
reducing our carbon footprint and moving away from fossil
fuel dependence.
Continued on page 6
The Catalyst Review
December 2023
3

The_Catalyst_Review_December_2023

Table of Contents for the Digital Edition of The_Catalyst_Review_December_2023