Towards a better understanding of alkene metathesis: elucidating the properties of the major metal carbene catalyst types
Date
2015Author
Du Toit, Jean I.
Van Sittert, Cornelia G.C.E.
Vosloo, Hermanus C.M.
Metadata
Show full item recordAbstract
The difference in activity of metal carbene
catalysts has a major influence on the efficiency and application
of these metal carbenes as metathesis catalysts.
The focus of this research is to examine the properties of
the major metal carbene catalyst types to understand the
general activity trend. A comparative investigation of the
foremost Fischer-, Tebbe-, Grubbs-, and Schrock-type
metal carbenes was done using a qualitative structure–activity
type computational method via principal component
analysis. The effect of the change in metal atom as well as
the change in ligands was specifically considered. Four
Fischer-, a Tebbe-, five Grubbs-, and a Schrock-type carbene
were investigated in this regard. Geometry
optimizations of all species were done at the GGA/PBE/
DNP level with Materials Studio DMol3 and subsequent
single-point energy calculations were done with Gaussian
at the PBEPBE level with the cc-pVQZ-type basis sets.
Results showed that the descriptors extracted by the principal
component analyses could successfully reproduce or
match the generalized trend for metathesis activity, highlighting
the importance of the frontier orbitals in the
metathesis reaction
URI
http://hdl.handle.net/10394/18490https://doi.org/10.1007/s00706-015-1491-y
https://link.springer.com/article/10.1007%2Fs00706-015-1491-y