Please use this identifier to cite or link to this item:
|Title:||Reactivity of the CpMn(CO)2-XR bond [X = Cl, Br]: A kinetic study using rapid-scan FTIR spectroscopy|
|Source:||Bengali, A.A., Fan, W.Y. (2008-11-10). Reactivity of the CpMn(CO)2-XR bond [X = Cl, Br]: A kinetic study using rapid-scan FTIR spectroscopy. Organometallics 27 (21) : 5488-5493. ScholarBank@NUS Repository. https://doi.org/10.1021/om8005036|
|Abstract:||The mechanism and energetics of the displacement of dihaloalkanes from the photolytically generated CpMn(CO)2-XR (X = Cl, Br) complexes by 2,6-lutidine have been studied using rapid-scan FTIR. The substitution reactions proceed through an Id mechanism, and theoretical calculations indicate that the Mn-XR bond is mostly broken in the transition state. Activation enthalpies of 16-17 kcal/mol for the Mn-ClR and 18-19 kcal/mol for the Mn-BrR complexes are only slightly lower than previous thermodynamic measurements of the Mn-haloalkane bond dissociation enthalpies. The rate of displacement of bromoalkanes was found to be ∼10 times slower than for the analogous chloroalkanes. Ab initio calculations suggest that this difference in reactivity is primarily due to a more stable interaction between the Mn center and bromoalkanes. © 2008 American Chemical Society.|
|Appears in Collections:||Staff Publications|
Show full item record
Files in This Item:
There are no files associated with this item.
checked on Feb 15, 2018
WEB OF SCIENCETM
checked on Feb 6, 2018
checked on Feb 20, 2018
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.