Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-3178
Kirchner, B; Reiher, M; Hille, A; Hutter, J; Hess, B A (2005). Car-Parrinello molecular dynamics study of the initial dinitrogen reduction step in Sellmann-type nitrogenase model complexes. Chemistry - A European Journal, 11(2):574-583.
We have studied reduction reactions for nitrogen fixation at Sellmann-type model complexes with Car-Parrinello simulation techniques. These dinuclear complexes are especially designed to emulate the so-called open-side FeMoco model. The main result of this work shows that in order to obtain the reduced species several side reactions have to be suppressed. These involve partial dissociation of the chelate ligands and hydrogen atom transfer to the metal center. Working at low temperature turns out to be one necessary pre-requisite in carrying out successful events. The successful events cannot be described by simple reaction coordinates. Complicated processes are involved during the initiation of the reaction. Our theoretical study emphasizes two experimental strategies which are likely to inhibit the side reactions. Clamping of the two metal fragments by a chelating phosphane ligand should prevent dissociation of the complex. Furthermore, introduction of tert-butyl substituents could improve the solubility and should thus allow usage of a wider range of (mild) acids, reductants, and reaction conditions.
|Item Type:||Journal Article, refereed, original work|
|Communities & Collections:||07 Faculty of Science > Institute of Physical Chemistry|
|Deposited On:||26 Mar 2009 10:49|
|Last Modified:||27 Nov 2013 19:26|
|Citations:||Web of Science®. Times cited: 20|
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