Browsing by Author "Wiessner, Tedd C"

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    Supporting Information for Ligand effects on Decarbonylation of Palladium-acyl Complexes
    (2020-10-22) Wiessner, Tedd C; Fosu, Samuel A; Parveen, Riffat; Vlaisavljevich, Bess; Tolman, William B; Rath, Nigam; wbtolman@wustl.edu; William, Tolman; University of South Dakota, Vlaisavljevich Lab; Washington University in Saint Louis, Tolman Lab, Department of Chemistry and Center for Sustainable Polymers
    These files contain primary data along with associated output from instrumentation supporting all results reported in "Ligand effects on Decarbonylation of Palladium-acyl Complexes". In this work we found: The influences of perturbations of supporting phosphine ligands on the dehydrative decarbonylation of (Ln)Pd(II)(Cl)-hydrocinnamoyl com-plexes (L = PtBu3, 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 trend in L: PtBu3 > 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: a stable intermediate forms after chloride abstraction, from which -hydride elimination is rate-determining, the low coordination number for the PtBu3 case lowers reaction barriers for all steps, and the trans disposition of two ligands for L = PPh3 contributes to low efficiency for styrene production in that case.