Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic101123y
Title: Ligand substitution from the (η5-DMP)Mn(CO) 2(Solv) [DMP = 2,5-dimethylpyrrole, Solv = solvent] complexes: To ring slip or not to ring slip?
Authors: Swennenhuis, B.H.G.
Poland, R.
Fan, W.Y. 
Darensbourg, D.J.
Bengali, A.A.
Issue Date: 16-Aug-2010
Source: Swennenhuis, B.H.G., Poland, R., Fan, W.Y., Darensbourg, D.J., Bengali, A.A. (2010-08-16). Ligand substitution from the (η5-DMP)Mn(CO) 2(Solv) [DMP = 2,5-dimethylpyrrole, Solv = solvent] complexes: To ring slip or not to ring slip?. Inorganic Chemistry 49 (16) : 7597-7604. ScholarBank@NUS Repository. https://doi.org/10.1021/ic101123y
Abstract: The mechanism and energetics of the displacement of solvent from photolytically generated (η5-DMP)Mn(CO)2(Solv) complexes has been studied [DMP = 2,5-dimethylpyrrole, Solv = solvent]. Rate enhancement relative to the η5-cyclopentadienyl (Cp) system is not observed in the displacement of weakly bound solvents. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed density functional theory (DFT) calculations. The results indicate that for both the Cp and the DMP based systems the displacement of weakly bound solvents proceeds by a dissociative or Id mechanism. This is in sharp contrast to CO displacement from (η5-DMP)Mn(CO) 3, which is known to proceed by an associative mechanism by way of an η3 ring slip intermediate. The associative substitution pathway only becomes competitive with the dissociative channel when the Mn-Solv bond dissociation enthalpy is more than 33 kcal/mol. © 2010 American Chemical Society.
Source Title: Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/94150
ISSN: 00201669
DOI: 10.1021/ic101123y
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

5
checked on Mar 26, 2018

WEB OF SCIENCETM
Citations

5
checked on Mar 26, 2018

Page view(s)

24
checked on Mar 11, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.