Synthesis of zirconocene amides and ketimides and an investigation into their ethylene polymerization activity

K.W. Henderson, A. Hind, A.R. Kennedy, A.E. McKeown, R.E. Mulvey

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The zirconocene amide [Cp2Zr(Cl)N(CH2Ph)(2)] (5), and the zirconbcene ketimides [Cp2Zr(Cl)N=C(Bu')Ph] (7), and [Cp2Zr(Cl)N=C(NMe2)(2)] (9), have been prepared by the transmetallation reactions between the appropriate lithiated organonitrogen compounds and zirconocene dichloride (2). In addition, their methylated derivatives [Cp2Zr(Me)N(CH2Ph)(2)] (6), [Cp2Zr(Me)N=C(Bu')Ph] (8), and [Cp2Zr(Me)N=C(NMe2)(2)] (10), have been prepared by the reaction of each of the complexes 5, 7 and 9 with MeLi. Compounds 5 and 7 have been characterized by X-ray crystallography and the structure of the cocrystalline complex [Cp2Zr(Cl)N=C(Bu)Ph](0.4)[Cp2Zr(Me)N=C(Bu')Ph](0.6) (14), has similarly been determined. All of the complexes 5-10 are active catalysts for the polymerization of ethylene in the presence of a MAO cocatalyst. In contrast, no polymer was produced using B(C6F5)(3) as an activator, indicating that direct alkene insertion into the Zr-N bonds does not occur.
Original languageEnglish
Pages (from-to)63-70
Number of pages7
JournalJournal of Organometallic Chemistry
Volume656
Issue number1-2
DOIs
Publication statusPublished - 15 Aug 2002

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X ray crystallography
Amides
Polymerization
amides
Olefins
Ethylene
ethylene
polymerization
Derivatives
Catalysts
Monoamine Oxidase
Alkenes
Polymers
synthesis
dichlorides
X Ray Crystallography
alkenes
crystallography
insertion
catalysts

Keywords

  • zirconium
  • amides
  • ketimides
  • catalysis
  • polymerization

Cite this

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title = "Synthesis of zirconocene amides and ketimides and an investigation into their ethylene polymerization activity",
abstract = "The zirconocene amide [Cp2Zr(Cl)N(CH2Ph)(2)] (5), and the zirconbcene ketimides [Cp2Zr(Cl)N=C(Bu')Ph] (7), and [Cp2Zr(Cl)N=C(NMe2)(2)] (9), have been prepared by the transmetallation reactions between the appropriate lithiated organonitrogen compounds and zirconocene dichloride (2). In addition, their methylated derivatives [Cp2Zr(Me)N(CH2Ph)(2)] (6), [Cp2Zr(Me)N=C(Bu')Ph] (8), and [Cp2Zr(Me)N=C(NMe2)(2)] (10), have been prepared by the reaction of each of the complexes 5, 7 and 9 with MeLi. Compounds 5 and 7 have been characterized by X-ray crystallography and the structure of the cocrystalline complex [Cp2Zr(Cl)N=C(Bu)Ph](0.4)[Cp2Zr(Me)N=C(Bu')Ph](0.6) (14), has similarly been determined. All of the complexes 5-10 are active catalysts for the polymerization of ethylene in the presence of a MAO cocatalyst. In contrast, no polymer was produced using B(C6F5)(3) as an activator, indicating that direct alkene insertion into the Zr-N bonds does not occur.",
keywords = "zirconium, amides, ketimides, catalysis, polymerization",
author = "K.W. Henderson and A. Hind and A.R. Kennedy and A.E. McKeown and R.E. Mulvey",
year = "2002",
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day = "15",
doi = "10.1016/S0022-328X(02)01559-0",
language = "English",
volume = "656",
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Synthesis of zirconocene amides and ketimides and an investigation into their ethylene polymerization activity. / Henderson, K.W.; Hind, A.; Kennedy, A.R.; McKeown, A.E.; Mulvey, R.E.

In: Journal of Organometallic Chemistry, Vol. 656, No. 1-2, 15.08.2002, p. 63-70.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis of zirconocene amides and ketimides and an investigation into their ethylene polymerization activity

AU - Henderson, K.W.

AU - Hind, A.

AU - Kennedy, A.R.

AU - McKeown, A.E.

AU - Mulvey, R.E.

PY - 2002/8/15

Y1 - 2002/8/15

N2 - The zirconocene amide [Cp2Zr(Cl)N(CH2Ph)(2)] (5), and the zirconbcene ketimides [Cp2Zr(Cl)N=C(Bu')Ph] (7), and [Cp2Zr(Cl)N=C(NMe2)(2)] (9), have been prepared by the transmetallation reactions between the appropriate lithiated organonitrogen compounds and zirconocene dichloride (2). In addition, their methylated derivatives [Cp2Zr(Me)N(CH2Ph)(2)] (6), [Cp2Zr(Me)N=C(Bu')Ph] (8), and [Cp2Zr(Me)N=C(NMe2)(2)] (10), have been prepared by the reaction of each of the complexes 5, 7 and 9 with MeLi. Compounds 5 and 7 have been characterized by X-ray crystallography and the structure of the cocrystalline complex [Cp2Zr(Cl)N=C(Bu)Ph](0.4)[Cp2Zr(Me)N=C(Bu')Ph](0.6) (14), has similarly been determined. All of the complexes 5-10 are active catalysts for the polymerization of ethylene in the presence of a MAO cocatalyst. In contrast, no polymer was produced using B(C6F5)(3) as an activator, indicating that direct alkene insertion into the Zr-N bonds does not occur.

AB - The zirconocene amide [Cp2Zr(Cl)N(CH2Ph)(2)] (5), and the zirconbcene ketimides [Cp2Zr(Cl)N=C(Bu')Ph] (7), and [Cp2Zr(Cl)N=C(NMe2)(2)] (9), have been prepared by the transmetallation reactions between the appropriate lithiated organonitrogen compounds and zirconocene dichloride (2). In addition, their methylated derivatives [Cp2Zr(Me)N(CH2Ph)(2)] (6), [Cp2Zr(Me)N=C(Bu')Ph] (8), and [Cp2Zr(Me)N=C(NMe2)(2)] (10), have been prepared by the reaction of each of the complexes 5, 7 and 9 with MeLi. Compounds 5 and 7 have been characterized by X-ray crystallography and the structure of the cocrystalline complex [Cp2Zr(Cl)N=C(Bu)Ph](0.4)[Cp2Zr(Me)N=C(Bu')Ph](0.6) (14), has similarly been determined. All of the complexes 5-10 are active catalysts for the polymerization of ethylene in the presence of a MAO cocatalyst. In contrast, no polymer was produced using B(C6F5)(3) as an activator, indicating that direct alkene insertion into the Zr-N bonds does not occur.

KW - zirconium

KW - amides

KW - ketimides

KW - catalysis

KW - polymerization

UR - http://dx.doi.org/10.1016/S0022-328X(02)01559-0

U2 - 10.1016/S0022-328X(02)01559-0

DO - 10.1016/S0022-328X(02)01559-0

M3 - Article

VL - 656

SP - 63

EP - 70

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -