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Managing Editor  | July 2017

Scientists develop room temperature reaction to create chemical feedstock


A team of scientists from the Center for Hydrocarbon Functionalizations at the Institute for Basic Science (IBS) in Daejon, South Korea were able to produce olefins (molecules with a double bond between two carbon atoms) through dehydrogenation of methane and ethane with a titanium catalyst at lower temperatures than previously possible.

 

ibs_600

Olefins, that is molecules with a double bond between carbons (C=C, green box) are generated
from unreactive molecules of natural gases (violet box). (Institute for Basic Science)

 

According to a report on the IBS website, the scientists carried out the reaction, which removes hydrogen from methane or ethane to create the double bond between carbon atoms, at 75°C.

 

Previous attempts at this process used iridium, a much more expensive catalyst, and needed temperatures as high as 800°C. The original method also released carbon dioxide as a byproduct.

 

“The study showed that making olefins in a cheap, energy efficient way is possible,” the report continued. “The reaction can be performed at low temperature and the titanium catalyst can be partially recycled, so it can be used again to dehydrogenate more natural gas. The next challenge of the research team is to make the titanium-based catalyst more efficient.”

 

The work was recently published in Nature Chemistry. The abstract read:

 

“Selectively converting linear alkanes to α-olefins under mild conditions is a highly desirable transformation given the abundance of alkanes as well as the use of olefins as building blocks in the chemical community.

 

“Until now, this reaction has been primarily the remit of noble-metal catalysts, despite extensive work showing that base-metal alkylidenes can mediate the reaction in a stoichiometric fashion. Here, we show how the presence of a hydrogen acceptor, such as the phosphorus ylide, when combined with the alkylidene complex (PNP)Ti=CHtBu(CH3) (PNP=N[2-P(CHMe2)2-4-methylphenyl]2), catalyses the dehydrogenation of cycloalkanes to cyclic alkenes, and linear alkanes with chain lengths of C4 to C8 to terminal olefins under mild conditions.

 

“This Article represents the first example of a homogeneous and selective alkane dehydrogenation reaction using a base-metal titanium catalyst.

 

“We also propose a unique mechanism for the transfer dehydrogenation of hydrocarbons to olefins and discuss a complete cycle based on a combined experimental and computational study.”

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