Quantum Chemical Investigations of Reaction Paths of Metalloenzymes and Biomimetic Models – The Hydrogenase Example

2006 ◽  
pp. 1-46 ◽  
Author(s):  
Luca Bertini ◽  
Maurizio Bruschi ◽  
Luca de Gioia ◽  
Piercarlo Fantucci ◽  
Claudio Greco ◽  
...  
Keyword(s):  
Quantum Chemical ◽  
Reaction Paths ◽  
Biomimetic Models

scholarly journals The quantum-chemical basis of the catalytic reactivity of transition metals

1992 ◽  
Vol 341 (1661) ◽  
pp. 269-282 ◽  
Keyword(s):  
Quantum Chemical ◽  
Oxidation Reaction ◽  
Active Sites ◽  
State Of The Art ◽  
Reaction Paths ◽  
Chemical Methods ◽  
Quantum Chemical Methods ◽  
Co Dissociation ◽  
Catalytically Active ◽  
Catalytic Reactivity

State of the art computational quantum-chemical methods enable the modelling of catalytically active sites with an accuracy of relevance to chemical predictability. This opens the possibility to predict reaction paths of elementary reaction steps on catalytically active surfaces. The results of such an approach are illustrated for a few dissociation and association reactions as they occur on transition metal surfaces. Examples to be given concern CO dissociation, carbon-carbon coupling and NH 3 oxidation. Reaction paths appear to be controlled by the principle of minimum surface atom sharing.

Unusual reaction paths of SN2 nucleophile substitution reactions CH4+H−→CH4+H− and CH4+F−→CH3F+H−: Quantum chemical calculations

2013 ◽  
Vol 425 ◽  
pp. 170-176 ◽  
Author(s):  
Ruslan M. Minyaev ◽  
Wolfgang Quapp ◽  
Benjamin Schmidt ◽  
Ilya V. Getmanskii ◽  
Vitaliy V. Koval
Keyword(s):  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Unusual Reaction ◽  
Reaction Paths ◽  
Substitution Reactions

Breaking the NO bond on Rh, Pd, and Pd3Mn alloy (100) surfaces: A quantum chemical comparison of reaction paths

2001 ◽  
Vol 115 (17) ◽  
pp. 8101-8111 ◽  
Author(s):  
D. Loffreda ◽  
F. Delbecq ◽  
D. Simon ◽  
P. Sautet
Keyword(s):  
Quantum Chemical ◽  
Reaction Paths

A quantum-chemical study of dehydration of ortho forms of formaldehyde and formic acid

1986 ◽  
Vol 51 (9) ◽  
pp. 1819-1833 ◽  
Author(s):  
Jaroslav Leška ◽  
Eugen Németh ◽  
Dušan Loos
Keyword(s):  
Oxygen Atom ◽  
Water Molecule ◽  
Formic Acid ◽  
Gas Phase ◽  
Quantum Chemical ◽  
Quantum Chemical Study ◽  
Chemical Study ◽  
Reaction Paths ◽  
Full Optimization ◽  
Acid Catalyzed

Gas-phase dehydration of methanediol (I) and methanetriol (II) has been studied by the MINDO/3 method with full optimization of the reaction paths. The intramolecular dehydration goes via high barriers (I 257.4, II 193.3 kJ mol-1). The acid-catalyzed dehydration involving protonation at oxygen atom of I goes via a considerably lower barrier (63.3 kJ mol-1), whereas protonation at oxygen atom of II results in practically spontaneous dehydration (0.4 kJ mol-1), which is the reason for the formic acid not being hydrated in water. Deprotonation of the protonated formaldehyde (II) and protonated formic acid (IV) is connected with high barriers (429.1 and 523.0 kJ mol-1, resp.). The deprotonation by a water molecule added to III and IV involves substantially lower barriers (53.9 and 96.3 kJ mol-1, resp.).

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