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Synthesis of Allylnickel Aryloxides and Arenethiolates: Study of Their Dynamic Isomerization and 1,3-Diene Polymerization Activity

Hampton, Philip D. and Wu, Si and Alam, Todd M. and Claverie, Jerome P. (1994) Synthesis of Allylnickel Aryloxides and Arenethiolates: Study of Their Dynamic Isomerization and 1,3-Diene Polymerization Activity. Organometallics, 13 (5). pp. 2066-2074. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20180521-130959588

[img] PDF (^(19)F NMR spectra for complexes 5 and 8 along with the computer-simulated spectra, a table of ^(19)F coupling constants for these complexes, and a solid-state ^(13)-CPMAS NMR spectrum of poly(CHD) obtained from initiator 5 (4 pages)) - Supplemental Material
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Abstract

A new family of allylnickel(I1) complexes, [Ni(η^3-+allyl)(µ-X)]_2 (X = ArO, ArS), have been synthesized by anion metathesis of the sodium or lithium salts of aryloxides or arenethiolates with [Ni(η^3-allyl)(µ-Br)]_2. The complexes are proposed to be dimeric and to consist of a mixture of cis and trans isomers. A dynamic process rapidly equilibrates the cis and trans isomers of the pentafluorophenoxide, 2,6-difluorophenoxide, and 3,5-bis(trifluoromethyl)phenoxide complexes on the ^1H NMR time scale. The 2,6-dimethylphenoxide, 2,6-diisopropylphenoxide, 2,4,6- tris(trifluoromethyl)phenoxide, and pentafluorothiophenoxide complexes are static at room temperature. A variable-temperature NMR study of the 3,5-bis(trifluoromethyl)phenoxide complex provided activation enthalpy and entropy values of 12.9 kcal/mol and -6.6 cal/ (K mol), respectively. Allyl rotation or cleavage of one of the µ-X bridges is proposed as the mechanism for the isomerization. The pentafluorophenoxide, 3,5-bis(trifluoromethyl)phenoxide, and 2,4,6-tris(trifluoromethy1)phenoxide complexes initiate the rapid polymerization of 1,3-cyclohexadiene and 1,3-butadiene to form high-molecular weight, 1,4-linked polymers.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/om00017a073DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/om00017a073PublisherSupporting Information
Additional Information:© 1994 American Chemical Society. Received November 1, 1993. We gratefully acknowledge Prof. Robert H. Grubbs for many helpful discussions. The Air Force Office of Scientific Research is acknowledged for providing financial assistance to J.P.C. We thank Dr. Roger Assink and Ralph H. Hunkins at Sandia National Laboratories for providing ^(13)C-CPMAS NMR spectra of poly(CHD). We acknowledge the NSF Chemical Instrumentation Program for providing a low-field NMR spectrometer.
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Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
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Issue or Number:5
Record Number:CaltechAUTHORS:20180521-130959588
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180521-130959588
Official Citation:Synthesis of Allylnickel Aryloxides and Arenethiolates: Study of Their Dynamic Isomerization and 1,3-Diene Polymerization Activity Philip D. Hampton, Si Wu, Todd M. Alam, and Jerome P. Claverie Organometallics 1994 13 (5), 2066-2074 DOI: 10.1021/om00017a073
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86504
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:21 May 2018 20:21
Last Modified:03 Oct 2019 19:44

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