“…The molecular nature of diacetates enables their motion across the network of highly abundant physisorbed H-bonded acetic acid (1757 cm –1 , Figure a) between SiO 2 particles. , Pd and Cu diacetates are known to decompose before melting or vaporizing, , which suggests that a reactive environment is needed to repeatedly reform these species during restructuring. Under these conditions, the mobility would require the solvation of diacetate clusters by acetic acid layers, and some connectivity in these layers across SiO 2 particles would be expected.…”
We demonstrate that single-atom alloy catalysts can be made by exposing physical mixtures of monometallic supported Cu and Pd catalysts to vinyl acetate (VA) synthesis reaction conditions. This reaction induces the formation of mobile clusters of metal diacetate species that drive extensive metal nanoparticle restructuring, leading to atomic dispersion of the precious metal, smaller nanoparticle sizes than the parent catalysts, and high activity and selectivity for both VA synthesis and ethanol dehydrogenation reactions. This approach is scalable and appears to be generalizable to other alloy catalysts.
“…The molecular nature of diacetates enables their motion across the network of highly abundant physisorbed H-bonded acetic acid (1757 cm –1 , Figure a) between SiO 2 particles. , Pd and Cu diacetates are known to decompose before melting or vaporizing, , which suggests that a reactive environment is needed to repeatedly reform these species during restructuring. Under these conditions, the mobility would require the solvation of diacetate clusters by acetic acid layers, and some connectivity in these layers across SiO 2 particles would be expected.…”
We demonstrate that single-atom alloy catalysts can be made by exposing physical mixtures of monometallic supported Cu and Pd catalysts to vinyl acetate (VA) synthesis reaction conditions. This reaction induces the formation of mobile clusters of metal diacetate species that drive extensive metal nanoparticle restructuring, leading to atomic dispersion of the precious metal, smaller nanoparticle sizes than the parent catalysts, and high activity and selectivity for both VA synthesis and ethanol dehydrogenation reactions. This approach is scalable and appears to be generalizable to other alloy catalysts.
“…Efforts to expand the scope of palladium‐catalyzed allylic oxidation to incorporate other carboxylate groups have encountered several limitations. Pd(OAc) 2 is one of the most common commercially available Pd II sources and, therefore, is the most prevalent Pd source for allylic oxidation, among other reactions . Szabó and co‐workers reported two strategies for acyloxylation catalyzed by Pd(OAc) 2 : (a) using 4 equivalents of carboxylic anhydride or (b) incorporating the carboxylate source into their oxidant by utilizing 3–3.5 equivalents of a hypervalent iodine oxidant with the corresponding lithium carboxylate salt .…”
Section: Methodsmentioning
confidence: 99%
“…Pd(OAc) 2 is one of the most common commercially availableP d II sources and, therefore, is the most prevalent Pd source for allylic oxidation, [9,10] among other reactions. [11] Szabó and co-workersr eported two strategies for acyloxylation catalyzed by Pd(OAc) 2 :( a) using 4equivalents of carboxylic anhydride [9b] or (b) incorporating the carboxylate sourcei nto their oxidant by utilizing 3-3.5 equivalents of ah ypervalent iodine oxidantw ith the corresponding lithium carboxylate salt. [6a,10] Hartwig and co-workersu sed stoichiometric tert-butylbenzoyl peroxide and Pd II benzoate to form allylb enzoates, reducing carboxylate loading to 2equivalents.…”
Scheme1.a) Generalm ethod for allylic acetoxylation using Pd(OAc) 2 as the catalyst and AcOH as the solvent or cosolvent. b) Prior approaches to allylic acyloxylation using either Pd(OAc) 2 or Pd(OBz) 2 as the catalyst and the carboxylate in high quantitieso ri ncorporated through the oxidant.c )T wo approaches for the use of low-stoichiometry carboxylic acid using palladium sourceswith noncoordinatinganions.[a] C.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.