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Design of a highly active Pd catalyst with P,N hemilabile ligands for alkoxycarbonylation of alkynes and allenes : a density functional theory study
Item metadata
dc.contributor.author | Ahmad, Shahbaz | |
dc.contributor.author | Buehl, Michael | |
dc.date.accessioned | 2020-08-13T23:36:38Z | |
dc.date.available | 2020-08-13T23:36:38Z | |
dc.date.issued | 2019-09-06 | |
dc.identifier | 259680425 | |
dc.identifier | 277a52dc-ddac-4f4c-b144-3a7cb563dc75 | |
dc.identifier | 85070957017 | |
dc.identifier | 000481245000001 | |
dc.identifier.citation | Ahmad , S & Buehl , M 2019 , ' Design of a highly active Pd catalyst with P,N hemilabile ligands for alkoxycarbonylation of alkynes and allenes : a density functional theory study ' , Chemistry - A European Journal , vol. 25 , no. 50 , pp. 11625-11629 . https://doi.org/10.1002/chem.201902402 | en |
dc.identifier.issn | 0947-6539 | |
dc.identifier.other | ORCID: /0000-0002-1095-7143/work/60630500 | |
dc.identifier.uri | https://hdl.handle.net/10023/20461 | |
dc.description | Authors thanks EaStCHEM and the School of Chemistry for support. | en |
dc.description.abstract | In palladium-catalysed methoxycarbonylation of technical propyne, the presence of propadiene poisons the hemilabile Pd(P,N) catalyst. According to density functional theory calculations (B3PW91-D3/PCM level), a highly stable π-allyl intermediate is the reason for this catalyst poisoning. Predicted regioselectivities suggest that at least 11% of propadiene should yield this allyl intermediate, where the reaction gets stalled under the turnover conditions due to an insurmountable methanolysis barrier of 25.8 kcal mol-1. Results obtained for different ligands and substrates are consistent with the available experimental data. A new ligand, (6-Cl-3-Me-Py)PPh2, is proposed, which is predicted to efficiently control the branched/linear selectivity, avoiding rapid poisoning (with only 0.2% of propadiene being trapped as Pd allyl complex), and to tremendously increase the catalytic activity by decreasing the overall barrier to 9.1 kcal mol-1. | |
dc.format.extent | 345398 | |
dc.language.iso | eng | |
dc.relation.ispartof | Chemistry - A European Journal | en |
dc.subject | Homogeneous catalysis | en |
dc.subject | DFT computations | en |
dc.subject | Reaction mechanisms | en |
dc.subject | Rational ligand design | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject | BDC | en |
dc.subject.lcc | QD | en |
dc.title | Design of a highly active Pd catalyst with P,N hemilabile ligands for alkoxycarbonylation of alkynes and allenes : a density functional theory study | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | 10.1002/chem.201902402 | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2020-08-14 |
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