First-principles simulations of C-S bond cleavage in rhenium thioether complexes

Journal of Physical Chemistry A

Volumn 108, Issue 11, 2004, Pages 2008-2013

  Magistrato, Alessandra ^a   Maurer, Patrick ^a   Fässler, Thomas ^b   Rothlisberger, Ursula ^a,c  

^a LABORATORY OF INORGANIC CHEMISTRY   (Switzerland)

^b DARMSTADT UNIVERSITY OF TECHNOLOGY   (Germany)

^c EPFL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; BOND STRENGTH (CHEMICAL); COMPUTER SIMULATION; DISSOCIATION; ELECTRON TRANSPORT PROPERTIES; ELECTRONIC STRUCTURE; REDUCTION; RHENIUM COMPOUNDS; TEMPERATURE;

BOND CLEAVAGE; BOND DISSOCIATION; RHENIUM THIOETHER COMPLEXES;

MOLECULAR DYNAMICS;

EID: 1642276867     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp037932k     Document Type: Article

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35. The bond orders reported in the Table 3 are calculated with the BLYP functional on structures that have been optimized at the same level. Calculations of the bond orders have been done according to the scheme proposed by Mayer, I. Chem. Phys. Lett. 1983, 97, 270. To this end, the plane wave representation of the total wave functions was projected onto an atom-centered minimal basis of atomic pseudo wave functions. This allows a comparison of the bond orders at a qualitative level.
36. For the oxidized pathway the dissociation limit calculated with the BP functional (22.1 kcal/mol) is 1.6 kcal/mol above the transition state (20.5 kcal/mol). Following the reaction pathway and analyzing the average constraint force we identified a very shallow minimum after the transition state in which the ethene is still weakly coordinated to the central metal. This minimum is stabilized by only 1.2 kcal/mol with respect to a barrier recrossing back to the reactants.
37. Increasing the temperature of the system allows for an enhanced sampling of the potential energy surface, which makes it possible to follow reaction pathways within the limited time of our simulations (typically of the order of a few tens of picoseconds).
38. In the fourth frame we do not show the ethene molecule that is still present in the simulation cell.