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Dialkyl and Methyl-Alkyl Zirconocenes: Synthesis and Characterization of Zirconocene-Alkyls That Model the Polymeryl Chain in Alkene Polymerizations

Klamo, Sara B; Wendt, Ola LU ; Henling, Larry M; Day, Michael W. and Bercaw, John E (2007) In Organometallics 26(12). p.3018-3030
Abstract
Zirconocene precatalysts with sterically bulky alkyl groups were designed as model systems for the propagating species in zirconocene-catalyzed alkene polymerization. Specialty alkyllithium reagents Li(CH2CEt3) and Li(CH2CMe2CH2Ph) were prepared and utilized in the synthesis of dialkyl and methyl-alkyl zirconocenes of the form CpCp*ZrR2, Cp2Zr(CH3)(R), and CpCp*Zr(CH3)(R) (Cp = (5-C5H5); Cp* = (5-C5Me5); R = CH2CMe3, CH2SiMe3, CH2CEt3, CH2CMe2CH2Ph). These new zirconocene alkyls were isolated and fully characterized by NMR spectroscopy and in some cases by X-ray diffraction. The molecular structures determined display the bent-sandwich coordination mode common for zirconocenes. The steric influence of the alkyl group on the observed... (More)
Zirconocene precatalysts with sterically bulky alkyl groups were designed as model systems for the propagating species in zirconocene-catalyzed alkene polymerization. Specialty alkyllithium reagents Li(CH2CEt3) and Li(CH2CMe2CH2Ph) were prepared and utilized in the synthesis of dialkyl and methyl-alkyl zirconocenes of the form CpCp*ZrR2, Cp2Zr(CH3)(R), and CpCp*Zr(CH3)(R) (Cp = (5-C5H5); Cp* = (5-C5Me5); R = CH2CMe3, CH2SiMe3, CH2CEt3, CH2CMe2CH2Ph). These new zirconocene alkyls were isolated and fully characterized by NMR spectroscopy and in some cases by X-ray diffraction. The molecular structures determined display the bent-sandwich coordination mode common for zirconocenes. The steric influence of the alkyl group on the observed structural parameters is reflected in slightly expanded C-Zr-C or C-Zr-Cl angles in the equatorial plane and long zirconium-alkyl bond distances. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
26
issue
12
pages
3018 - 3030
publisher
The American Chemical Society
external identifiers
  • scopus:34250766055
ISSN
1520-6041
DOI
10.1021/om0601302
language
English
LU publication?
yes
id
97f46865-5d7b-460e-a8e2-44503682af85 (old id 947117)
date added to LUP
2008-01-25 12:24:04
date last changed
2017-01-01 04:42:55
@article{97f46865-5d7b-460e-a8e2-44503682af85,
  abstract     = {Zirconocene precatalysts with sterically bulky alkyl groups were designed as model systems for the propagating species in zirconocene-catalyzed alkene polymerization. Specialty alkyllithium reagents Li(CH2CEt3) and Li(CH2CMe2CH2Ph) were prepared and utilized in the synthesis of dialkyl and methyl-alkyl zirconocenes of the form CpCp*ZrR2, Cp2Zr(CH3)(R), and CpCp*Zr(CH3)(R) (Cp = (5-C5H5); Cp* = (5-C5Me5); R = CH2CMe3, CH2SiMe3, CH2CEt3, CH2CMe2CH2Ph). These new zirconocene alkyls were isolated and fully characterized by NMR spectroscopy and in some cases by X-ray diffraction. The molecular structures determined display the bent-sandwich coordination mode common for zirconocenes. The steric influence of the alkyl group on the observed structural parameters is reflected in slightly expanded C-Zr-C or C-Zr-Cl angles in the equatorial plane and long zirconium-alkyl bond distances.},
  author       = {Klamo, Sara B and Wendt, Ola and Henling, Larry M and Day, Michael W. and Bercaw, John E},
  issn         = {1520-6041},
  language     = {eng},
  number       = {12},
  pages        = {3018--3030},
  publisher    = {The American Chemical Society},
  series       = {Organometallics},
  title        = {Dialkyl and Methyl-Alkyl Zirconocenes: Synthesis and Characterization of Zirconocene-Alkyls That Model the Polymeryl Chain in Alkene Polymerizations},
  url          = {http://dx.doi.org/10.1021/om0601302},
  volume       = {26},
  year         = {2007},
}