Taming the shrew: [TMEDALi-Zn(C2H4)(2)L] as a model compound for anionic ethene polymerisation

Joerg Sassmannshausen, Jan Klett, Alan R. Kennedy, John A. Parkinson, David Armstrong

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

We describe the synthesis of the compound [(TMEDA)Li(mu-TMP)(mu-CH=CH2)Zn(C2H3)] (1) (TMEDA = N,N,N',N'-tetramethylethylenediamine, TMP = 2,2,6,6-tetramethylpiperidide), which serves as a potential model compound for anionic ethene polymerisation, and its decomposition into the metallated compound [Li(mu-Me2NCH2CH2N(Me)CH2)(mu-TMP)Zn(C2H3)] (4). The previously reported compound [(PMDETA)K(mu-TMP)(mu-CHQCH(2))-Zn(CH2SiMe3)] (2) (PMDETA = N,N,N',N '',N ''-pentamethyldiethylene-triamine) and 1 are used as potential model compounds for anionic ethene polymerisation. Detailed Density Functional Theory (DFT) at the B3LYP/6-311G(d,p) level of theory on both 1 and 2 in conjunction with Bader AIM and NBO analyses revealed a substantial interaction between the Zn-CH atom and the Li (in 1, d(Li-CH) = 2.43 angstrom) or K (in 2, d(K-CH) = 3.01 angstrom). In fact, in the case of 1, this interaction is even stronger (estimated to be 20-30 kJ mol(-1)) than those reported in the previously reported DFT studies of the reaction with butyl lithium and ethene in the presence of diamino ligands. Our theoretical results are in good agreement with experimentally observed parameters.

LanguageEnglish
Pages494-501
Number of pages8
JournalNew Journal of Chemistry
Volume37
Issue number2
Early online date19 Nov 2012
DOIs
Publication statusPublished - 2013

Fingerprint

Thymidine Monophosphate
Anionic polymerization
Density functional theory
Lithium
Ligands
Decomposition
Atoms
ethylene
phenyllithium

Keywords

  • taming the shrew
  • model compound
  • anionic ethene polymerisation
  • synthesis
  • TMEDA

Cite this

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title = "Taming the shrew: [TMEDALi-Zn(C2H4)(2)L] as a model compound for anionic ethene polymerisation",
abstract = "We describe the synthesis of the compound [(TMEDA)Li(mu-TMP)(mu-CH=CH2)Zn(C2H3)] (1) (TMEDA = N,N,N',N'-tetramethylethylenediamine, TMP = 2,2,6,6-tetramethylpiperidide), which serves as a potential model compound for anionic ethene polymerisation, and its decomposition into the metallated compound [Li(mu-Me2NCH2CH2N(Me)CH2)(mu-TMP)Zn(C2H3)] (4). The previously reported compound [(PMDETA)K(mu-TMP)(mu-CHQCH(2))-Zn(CH2SiMe3)] (2) (PMDETA = N,N,N',N '',N ''-pentamethyldiethylene-triamine) and 1 are used as potential model compounds for anionic ethene polymerisation. Detailed Density Functional Theory (DFT) at the B3LYP/6-311G(d,p) level of theory on both 1 and 2 in conjunction with Bader AIM and NBO analyses revealed a substantial interaction between the Zn-CH atom and the Li (in 1, d(Li-CH) = 2.43 angstrom) or K (in 2, d(K-CH) = 3.01 angstrom). In fact, in the case of 1, this interaction is even stronger (estimated to be 20-30 kJ mol(-1)) than those reported in the previously reported DFT studies of the reaction with butyl lithium and ethene in the presence of diamino ligands. Our theoretical results are in good agreement with experimentally observed parameters.",
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Taming the shrew : [TMEDALi-Zn(C2H4)(2)L] as a model compound for anionic ethene polymerisation. / Sassmannshausen, Joerg; Klett, Jan; Kennedy, Alan R.; Parkinson, John A.; Armstrong, David.

In: New Journal of Chemistry, Vol. 37, No. 2, 2013, p. 494-501.

Research output: Contribution to journalArticle

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AU - Sassmannshausen, Joerg

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AU - Parkinson, John A.

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