Forum for Science, Industry and Business

Sponsored by:     3M 
Search our Site:

 

Acetic acid as a proton shuttle in gold chemistry

29.07.2015

Scientists in Russian Academy of Sciences, Moscow have studied the mechanism of gold-mediated transformation of acetylenic molecules.

A recently published study by Ananikov and co-workers gives a vivid example of unusual chemical reactivity found in the reactions with organogold complexes. Using the complex of modern physical methods joined with computational studies, the authors proposed reaction mechanism, where a molecule of acetic acid serves as a proton shuttle, transferring the hydrogen atom between the reaction centers.


Carboxylic group-assisted proton transfer in metal complex. Copyright: Ananikov Laboratory (AnanikovLab.ru)

Being found mostly in the native state, gold is one of the oldest elements known to man. The affection to gold was determined by it's unusual properties – heft, shine and ability to withstand oxidation and corrosion. The combination of properties determined gold use in the jewelry and as a coinage metal.

The ancient alchemists working with gold were struggled by utmost chemical resistance of this element – it did not react with concentrated acids or alkali solutions even at high temperatures. Actually, it is the chemical inertness that makes gold to appear in a native form and not as a part of a mineral.

Later analysis established that gold compounds can not only compete with traditional nickel and palladium-based catalysts in the common reactions, but to surpass them. Besides that, gold compounds often demonstrated principally novel types of reactivity compared to well-established catalysts. This allowed chemists to discover a bunch of new chemical reactions and predetermined a fascinating boom in gold catalysis that we have observed in the recent years.

Professor Ananikov and co-workers introduced gold into well-known catalytic system which led to dramatic change of the reactivity and furnished the formation of novel gold-containing complexes. The complexes appeared to be air stable and were isolated in the individual state. A single crystal X-Ray diffraction study ascertained the existence of unique structural motif in the molecule, which can not be explained within conventional mechanistic framework.

The study was carried out using both theoretical and experimental approaches. Dedicated labeling of the reagents allowed observation of molecular re-organizations. Variation of reaction conditions helped to estimate key factors governing the discovered transformation.

In addition, computational study of the reaction provided the models of certain intermediate steps, which were invisible for experimental investigation. The theoretical data obtained was in excellent agreement with experiment, proposing the reaction mechanism, where a molecule of acetic acid serves as a proton shuttle, transferring the hydrogen atom between the reaction centers.

The belief of gold inactivity towards chemical transformations resulted in the fact, that organometallic chemistry of gold was developed significantly later compared to other coinage metals (like silver, nickel or copper). Today, our goal is to “introduce gold catalysis as a valuable practical tool in fine organic chemistry, competitive with other transition metal catalysts”, says Prof. Ananikov.


Reference:
S. S. Zalesskiy, V. N. Khrustalev, A. Yu. Kostukovich, and V. P. Ananikov, "Carboxylic Group-Assisted Proton Transfer in Gold-Mediated Thiolation of Alkynes", Organometallics, 2015, Article ASAP. DOI: 10.1021/acs.organomet.5b00210


Associated links
Professor Valentine Ananikov laboratory website
Read the paper on Organometallics

Ananikov Laboratory | ResearchSea
Further information:
http://zioc.ru/
http://www.researchsea.com

More articles from Life Sciences:

nachricht At last, butterflies get a bigger, better evolutionary tree
16.02.2018 | Florida Museum of Natural History

nachricht New treatment strategies for chronic kidney disease from the animal kingdom
16.02.2018 | Veterinärmedizinische Universität Wien

All articles from Life Sciences >>>

The most recent press releases about innovation >>>

Die letzten 5 Focus-News des innovations-reports im Überblick:

Im Focus: Demonstration of a single molecule piezoelectric effect

Breakthrough provides a new concept of the design of molecular motors, sensors and electricity generators at nanoscale

Researchers from the Institute of Organic Chemistry and Biochemistry of the CAS (IOCB Prague), Institute of Physics of the CAS (IP CAS) and Palacký University...

Im Focus: Hybrid optics bring color imaging using ultrathin metalenses into focus

For photographers and scientists, lenses are lifesavers. They reflect and refract light, making possible the imaging systems that drive discovery through the microscope and preserve history through cameras.

But today's glass-based lenses are bulky and resist miniaturization. Next-generation technologies, such as ultrathin cameras or tiny microscopes, require...

Im Focus: Stem cell divisions in the adult brain seen for the first time

Scientists from the University of Zurich have succeeded for the first time in tracking individual stem cells and their neuronal progeny over months within the intact adult brain. This study sheds light on how new neurons are produced throughout life.

The generation of new nerve cells was once thought to taper off at the end of embryonic development. However, recent research has shown that the adult brain...

Im Focus: Interference as a new method for cooling quantum devices

Theoretical physicists propose to use negative interference to control heat flow in quantum devices. Study published in Physical Review Letters

Quantum computer parts are sensitive and need to be cooled to very low temperatures. Their tiny size makes them particularly susceptible to a temperature...

Im Focus: Autonomous 3D scanner supports individual manufacturing processes

Let’s say the armrest is broken in your vintage car. As things stand, you would need a lot of luck and persistence to find the right spare part. But in the world of Industrie 4.0 and production with batch sizes of one, you can simply scan the armrest and print it out. This is made possible by the first ever 3D scanner capable of working autonomously and in real time. The autonomous scanning system will be on display at the Hannover Messe Preview on February 6 and at the Hannover Messe proper from April 23 to 27, 2018 (Hall 6, Booth A30).

Part of the charm of vintage cars is that they stopped making them long ago, so it is special when you do see one out on the roads. If something breaks or...

All Focus news of the innovation-report >>>

Anzeige

Anzeige

VideoLinks
Industry & Economy
Event News

2nd International Conference on High Temperature Shape Memory Alloys (HTSMAs)

15.02.2018 | Event News

Aachen DC Grid Summit 2018

13.02.2018 | Event News

How Global Climate Policy Can Learn from the Energy Transition

12.02.2018 | Event News

 
Latest News

Fingerprints of quantum entanglement

16.02.2018 | Information Technology

'Living bandages': NUST MISIS scientists develop biocompatible anti-burn nanofibers

16.02.2018 | Health and Medicine

Hubble sees Neptune's mysterious shrinking storm

16.02.2018 | Physics and Astronomy

VideoLinks
Science & Research
Overview of more VideoLinks >>>