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- W2314437660 abstract "This combined experimental and computational study demonstrates how a metal center can drastically influence the reactivity of a coordinated ligand. We found that the consecutive formation of zerovalent bimetallic complexes proceeds by fast η2-C═C coordination of only one Pd(PEt3)2 moiety, which then significantly slows down the subsequent reaction. Electronic effects induced by complexation of the first metal center have a major effect on the subsequent formation of the bimetallic complexes. These effects are reduced by partial fluorination of the bis(vinylpyridine)-arene ligand. The monometallic complexes display migration of the Pd(PEt3)2 moiety between the two olefinic bonds of the corresponding ligand, as indicated by various solution NMR experiments, including variable-temperature NMR spectroscopy, 2D 1H–1H exchange spectroscopy, and spin saturation transfer. Density functional theory studies were performed at the SMD(toluene)–PBE0+d(v3)/B2//B97D/B1 level of theory." @default.
- W2314437660 created "2016-06-24" @default.
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- W2314437660 date "2015-03-04" @default.
- W2314437660 modified "2023-10-16" @default.
- W2314437660 title "Generation of Mono- and Bimetallic Palladium Complexes and Mechanistic Insight into an Operative Metal Ring-Walking Process" @default.
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- W2314437660 doi "https://doi.org/10.1021/acs.organomet.5b00051" @default.
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