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Uncovering the mechanism of homogeneous methyl methacrylate formation with P,N chelating ligands and palladium : favored reaction channels and selectivities

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Buehl_2014_Org_Uncovering_AM.pdf (1.094Mb)
Date
26/01/2015
Author
Crawford, Luke
Cole-Hamilton, David John
Buehl, Michael
Keywords
QD Chemistry
NDAS
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Abstract
The catalytic alkoxycarbonylation of alkynes via palladium and P,N ligands, studied through a prototypical reaction involving propyne methoxycarbonylation yielding methyl methacrylate, has been explored at the B3PW91-D3/PCM level of density functional theory. Four different reaction routes have been probed in detail, spanning those involving one or two hemilabile P,N ligands and either hydride or carbomethoxy mechanisms. The cycle that is both energetically most plausible and congruent with experimental data involves Pd(0) and two P,N ligands acting co-catalytically in turn to shuffle protons via both protonation and deprotonation reactions. Other mechanisms proposed in the literature can be discounted because they would lead to insurmountable barriers or incorrect selectivities. For the preferred mechanism, the P,N ligand is found to be crucial in determining the strong regioselectivity and intrinsically controls the overall turnover of the catalytic cycle with moderate barriers (ΔG‡ of 20.1 to 22.9 kcal/mol) predicted. Furthermore, the necessary acidic conditions are rationalized via a potential dicationic channel.
Citation
Crawford , L , Cole-Hamilton , D J & Buehl , M 2015 , ' Uncovering the mechanism of homogeneous methyl methacrylate formation with P,N chelating ligands and palladium : favored reaction channels and selectivities ' , Organometallics , vol. 34 , no. 2 , pp. 438–449 . https://doi.org/10.1021/om500970k
Publication
Organometallics
Status
Peer reviewed
DOI
https://doi.org/10.1021/om500970k
ISSN
0276-7333
Type
Journal article
Rights
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/om500970k
Description
The authors would like to thank the University of St. Andrews School of Chemistry and EaStCHEM for support
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/7986

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