η3-Allylpalladiuin complexes from medium-ring cycloalkenes

Jean Marie Rosset; Matthew P. Glenn; John D. Cotton; Anthony C. Willis; Colin H.L. Kennard; Karl A. Byriel; Bruce H. Riches; William Kitching

doi:10.1021/om971132c

η³-Allylpalladiuin complexes from medium-ring cycloalkenes

Jean Marie Rosset, Matthew P. Glenn, John D. Cotton, Anthony C. Willis, Colin H.L. Kennard, Karl A. Byriel, Bruce H. Riches, William Kitching^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The dimeric η³-allylpalladium chloride complexes formed from various cycloalkenes (C₇-C₁₃) and some methyl- and tert-butyl-substituted cycloalkenes have been characterized by ¹H and ¹³C 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 η³-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 (ΔG ‡ ≈ 11 kcal/mol) is considered to involve a "cubic" η³-allylpalladium chloride tetramer.

Original language	English
Pages (from-to)	1968-1983
Number of pages	16
Journal	Organometallics
Volume	17
Issue number	10
DOIs	https://doi.org/10.1021/om971132c
Publication status	Published - 11 May 1998

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title = "η3-Allylpalladiuin complexes from medium-ring cycloalkenes",

abstract = "The dimeric η3-allylpalladium chloride complexes formed from various cycloalkenes (C7-C13) and some methyl- and tert-butyl-substituted cycloalkenes have been characterized by 1H and 13C 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 η3-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 (ΔG ‡ ≈ 11 kcal/mol) is considered to involve a {"}cubic{"} η3-allylpalladium chloride tetramer.",

author = "Rosset, {Jean Marie} and Glenn, {Matthew P.} and Cotton, {John D.} and Willis, {Anthony C.} and Kennard, {Colin H.L.} and Byriel, {Karl A.} and Riches, {Bruce H.} and William Kitching",

year = "1998",

month = may,

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doi = "10.1021/om971132c",

language = "English",

volume = "17",

pages = "1968--1983",

journal = "Organometallics",

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T1 - η3-Allylpalladiuin complexes from medium-ring cycloalkenes

AU - Rosset, Jean Marie

AU - Glenn, Matthew P.

AU - Cotton, John D.

AU - Willis, Anthony C.

AU - Kennard, Colin H.L.

AU - Byriel, Karl A.

AU - Riches, Bruce H.

AU - Kitching, William

PY - 1998/5/11

Y1 - 1998/5/11

N2 - The dimeric η3-allylpalladium chloride complexes formed from various cycloalkenes (C7-C13) and some methyl- and tert-butyl-substituted cycloalkenes have been characterized by 1H and 13C 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 η3-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 (ΔG ‡ ≈ 11 kcal/mol) is considered to involve a "cubic" η3-allylpalladium chloride tetramer.

AB - The dimeric η3-allylpalladium chloride complexes formed from various cycloalkenes (C7-C13) and some methyl- and tert-butyl-substituted cycloalkenes have been characterized by 1H and 13C 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 η3-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 (ΔG ‡ ≈ 11 kcal/mol) is considered to involve a "cubic" η3-allylpalladium chloride tetramer.

UR - http://www.scopus.com/inward/record.url?scp=0001532596&partnerID=8YFLogxK

U2 - 10.1021/om971132c

DO - 10.1021/om971132c

M3 - Article

SN - 0276-7333

VL - 17

SP - 1968

EP - 1983

JO - Organometallics

JF - Organometallics

IS - 10

ER -

η³-Allylpalladiuin complexes from medium-ring cycloalkenes

Abstract

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