η3-Allylpalladium Complexes from Medium-Ring Cycloalkenes

Autor:	John D. Cotton, William Kitching, Colin H. L. Kennard, KA Byriel, Bruce H. Riches, Matthew P. Glenn, Anthony C. Willis, Jean-Marie Rosset
Rok vydání:	1998
Předmět:	Stereochemistry Chemistry Organic Chemistry Nuclear magnetic resonance spectroscopy Ring (chemistry) Sesquiterpene Chloride Inorganic Chemistry chemistry.chemical_compound Tetramer medicine Physical and Theoretical Chemistry Cis–trans isomerism medicine.drug
Zdroj:	Organometallics. 17:1968-1983
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om971132c
Popis:	The dimeric eta(3)-allylpalladium chloride complexes formed from various cycloalkenes (C-7-C-13) and some methyl-and tert-butyl-substituted cycle alkenes have be en characterized by H-1 and C-13 NMR spectroscopy and in selected cases by X-ray crystallography. The formation of syn and anti isomers in the larger ring systems is demonstrated, and complexes with a rearranged ring system are formed from tert-butylcyclodecene and tert-butylcyclododecene. The sesquiterpene, carophyllene, is shown to form an eta(3)-allyl exocyclic complex, exclusively from the (E)-double bond. Cis and trans isomers, with respect to allyl group orientation in these halo-bridged dimers, have been identified by low-temperature (190K) NMR spectroscopy, and their interconversion (Delta G(double dagger) approximate to 11 kcal/mol) is considered to involve a "cubic" eta(3)-allylpalladium chloride tetramer.
Databáze:	OpenAIRE
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