11/10/2023 0 Comments Driving force for proton transfer![]() We have investigated homologous series of compounds and demonstrated an exponential decrease in the rate constant with increasing proton tunnelling distance ( JACS 2011, p. Hydrogen bonds involving the transferring proton has large effects on the rate that affects the proton tunnelling distance, and often also the anharmonicity of the proton potential. Tianfei Liu, Robin Tyburski, Shihuai Wang, Ricardo Fernández-Terán, Sascha Ott, Leif Hammarström* Tianfei Liu, Meiyuan Guo, Andreas Orthaber, Reiner Lomoth, Marcus Lundberg, Sascha Ott and Leif Hammarström*Įlucidating Proton-Coupled Electron Transfer Mechanisms of Metal Hydrides with Free-energy and Pressure Dependent Kinetics This complex was also the first example of a single compound that could undergo all three types of PCET mechanisms – concerted, electron-first or proton-first – by changing the oxidant strength.Īccelerating Proton-Coupled Electron Transfer of Metal Hydrides in Catalyst Model Reactions Marc Bourrez, Romain Steinmetz, Sascha Ott, Frederic Gloaguen and Leif Hammarström*īy appending internal base groups as proton acceptor to the complex (collaboration with Sascha Ott), we could show greatly accelerated PCET reactions by facilitated PCET – a direct kinetic demonstration of the effect on reactivity of the 2 nd coordination sphere. This is quite different from the hydrogen atom transfer (HAT) conventionally thought to occur in such reactions, and of great fundamental interest and practical importance for solar fuels catalysis and organic synthesis by (photo)redox catalysis.Ĭoncerted Proton-Coupled Electron Transfer from a Metal-Hydride Complex ![]() We demonstrated activation of rather non-polar metal-hydrides by concerted PCET for the first time. We argue that concerted reaction steps may result in lower barriers (overpotentials) in e.g. We work with experimental tools to distinguish step-wise and concerted PCET mechanisms, and determine conditions allowing for concerted reactions in multi-electron/-proton reactions. ![]() Many of these are multi-electron transfer reactions coupling several electrons and protons to form the products. These include biological energy conversion, DNA reproduction and repair, chemical water splitting, fuel cells and interfacial electron transfer of semiconductors. Proton-coupled electron transfer (PCET) has become recognized as a fundamental reaction of great importance in broad areas of chemistry and biology. ![]()
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