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- W2090210629 abstract "The reactions of [PdPfBr(NCMe)2] (Pf = C6F5) with stoichiometric amounts of 1,5-hexadiene, 1,6-heptadiene, or 1,7-octadiene at low temperature result in the formation of several (η1-η2-enyl)palladium complexes that isomerize sequentially at different temperatures depending on the ring size of the palladacycles (Tisom: 7.5- < 6.5- < 5.5-membered). These (η1-η2-enyl)palladium derivatives are intermediates in the Pd-migration process, arrested by coordination of the unattacked double bond. The final products of their isomerization are several isomeric Pf−(η3-allyl)palladium complexes (Pf = C6F5). The major allylic derivative in each case arises from Pd migration to the terminal double bond. Minor amounts of (η3-allyl)palladium complexes formed by double bond switches in the process of Pd migration are also seen, but this occurs only on putative 1,5- or 1,6-diene−hydrido−palladium intermediates. A small amount of cyclic organic derivatives coming from the cyclization of (η1-η2-enyl)palladium intermediates is detected in each case. The use of excess diolefin gives rise to additional (η3-allyl)palladium complexes without the Pf group and to the corresponding Pf-substituted linear dienes. These arise via displacement of the Pf dienes by the starting diolefin in a hydrido−palladium intermediate during the Pd-migration process." @default.
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- W2090210629 date "1997-09-01" @default.
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- W2090210629 title "Palladium Migration along Linear Carbon Chains: The Detection of η<sup>1</sup>-η<sup>2</sup>-Enyl Intermediates and the Study of Their Rearrangement" @default.
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- W2090210629 doi "https://doi.org/10.1021/om9703907" @default.
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