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- W2315917466 abstract "The thermolysis of Cp*W(NO)(Npt)(η3-CH2CHCHSiMe3) (1; Cp* = η5-C5Me5; Npt = CH2CMe3) in benzene at 55 °C generates three isomeric products having the composition Cp*W(NO)(H)(η3-Me3SiCHCHCHPh) (2). These are isomers of the expected Cp*W(NO)(Ph)(η3-Me3SiCHCHCH2) compound and result from an intramolecular Ph/allyl H exchange. Thermolysis of 2 in the presence of pyridine produces the η2-olefin pyridine adduct Cp*W(NO)(η2-Me3SiCH2CH═CHPh)(C5H5N) (3). However, when the same reaction is carried out in deuterobenzene with 10 equiv of pyridine, NMR spectroscopic data suggest that the meso hydrogen of the allyl ligand is exchanged for a deuterium atom before pyridine trapping occurs. The activation of fluorobenzenes (i.e., pentafluorobenzene, p-difluorobenzene, and o-difluorobenzene) by Cp*W(NO)(Npt)(η3-CH2CHCHSiMe3) has also been studied, and for these substrates, C–H bond activation occurs exclusively. Selectivity for the activation of these C–H bonds appears to be determined by sterics. Intramolecular migration ..." @default.
- W2315917466 created "2016-06-24" @default.
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- W2315917466 date "2012-11-06" @default.
- W2315917466 modified "2023-09-26" @default.
- W2315917466 title "Thermal Chemistry of a Tungsten Trimethylsilylallyl Complex in Benzene and Fluorobenzenes" @default.
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- W2315917466 doi "https://doi.org/10.1021/om300765e" @default.
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