Journal article
Ligand Effects on Decarbonylation of Palladium-Acyl Complexes
Organometallics, Vol.39(22), pp.3992-3998
11/23/2020
DOI: 10.1021/acs.organomet.0c00584
Abstract
The influences of perturbations of supporting phosphine ligands on the dehydrative decarbonylation of (L-n)Pd-II (Cl)-hydro-cinnamoyl complexes (L = (PBu3)-Bu-t, n = 1; L = PPh3, n = 2; L = dppe, n = 1) to yield styrene were studied through combined experiment and theory. Abstraction of chloride from the complexes by silver and zinc salts, as well as sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, enhanced the efficiency of styrene formation, according to the following trend in L: (PBu3)-Bu-t > dppe > PPh3. DFT calculations corroborated the experimental findings and provided insights into the ligand influences on reaction step barriers and transition state structures. Key findings include the following: a stable intermediate forms after chloride abstraction, from which beta-hydride elimination is most affected by ligand choice, the low coordination number for the (PBu3)-Bu-t case lowers reaction barriers for all steps, and the trans disposition of two ligands for L = PPh3 contributes to the low efficiency for styrene production in that case.
Details
- Title: Subtitle
- Ligand Effects on Decarbonylation of Palladium-Acyl Complexes
- Creators
- Tedd C. Wiessner - Washington University in St. LouisSamuel Asiedu Fosu - University of South DakotaRiffat Parveen - University of South DakotaNigam P. Rath - University of Missouri–St. LouisBess Vlaisavljevich - University of South DakotaWilliam B. Tolman - Washington University in St. Louis
- Resource Type
- Journal article
- Publication Details
- Organometallics, Vol.39(22), pp.3992-3998
- Publisher
- Amer Chemical Soc
- DOI
- 10.1021/acs.organomet.0c00584
- ISSN
- 0276-7333
- eISSN
- 1520-6041
- Number of pages
- 7
- Grant note
- 5P41GM103422; R24GM136766 / NIH; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA CHE-1901635 / NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation CHE-1626516 / NSF; National Science Foundation (NSF) CHE-1827756 / NSF-MRI Award; National Science Foundation (NSF); NSF - Office of the Director (OD)
- Language
- English
- Date published
- 11/23/2020
- Academic Unit
- Chemistry
- Record Identifier
- 9984618510202771
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