Amidosilylcyclopentadienyl monoalkyl zirconium compounds: evidence of a N-assisted 1,3-proton shift olefin isomerization mechanism
Authors
Petrisor, Cristina Elena; Royo Cantabrana, Eva; Cuenca Agreda, José Tomás; Gómez-Bengoa, EnriqueIdentifiers
Permanent link (URI): http://hdl.handle.net/10017/3832DOI: 10.1021/om900296a
ISSN: 0276-7333
Publisher
ACS Journal Publishing
Date
2009Bibliographic citation
Organometallics, 2009, v. 28, p. 4165-4169
Keywords
Isomerización
Organometálicos
Zirconio
Project
MAT2007-60997 (Ministerio de Educación y Ciencia)
S-0505/PPQ/0328 (Comunidad de Madrid)
CCG08-UAH/PPQ-4026 (Universidad de Alcalá)
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Publisher's version
http://dx.doi.org/10.1021/om900296aRights
© American Chemical Society, 2009
Access rights
info:eu-repo/semantics/openAccess
Abstract
New η5-cyclopentadienyl-η1-amido monoalkyl zirconium compounds of the type [ZrR(η5-
C5H4SiMe2-η1-NtBu)(η5-C5H4R0)] (R = Me, Bn; R0 =H, SiMe3, SiMe2CH2CHdCH2) have been
synthesized and fully characterized. Allyldimethylsilylcyclopentadienyl derivatives [ZrR(η5-C5H4SiMe2-η1-NtBu)(η5-C5H4SiMe2CH2CHdCH2)] isomerize the allyl fragment bound to the
cyclopentadienyl ring to give the corresponding [ZrR(η5-C5H4SiMe2-η1-NtBu)(η5-C5H4SiMe2CHdCHCH3)] compounds (R=Me, Bn). Experimental as well as DFT computational studies support an isomerization mechanism based on a N-assisted 1,3-proton shift.
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