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Issue 2, 2013
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Taming the shrew: [TMEDALi-Zn(C2H4)2L] as a model compound for anionic ethene polymerisation

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Abstract

We describe the synthesis of the compound [(TMEDA)Li(μ-TMP)(μ-CH[double bond, length as m-dash]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(μ-Me2NCH2CH2N(Me)CH2)(μ-TMP)Zn(C2H3)] (4). The previously reported compound [(PMDETA)K(μ-TMP)(μ-CH[double bond, length as m-dash]CH2)-Zn(CH2SiMe3)] (2) (PMDETA = N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) 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, dLi–CH = 2.43 Å) or K (in 2, dK–CH = 3.01 Å). 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.

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

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Publication details

The article was received on 27 Sep 2012, accepted on 17 Nov 2012 and first published on 19 Nov 2012


Article type: Paper
DOI: 10.1039/C2NJ40874K
Citation: New J. Chem., 2013,37, 494-501
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    Taming the shrew: [TMEDALi-Zn(C2H4)2L] as a model compound for anionic ethene polymerisation

    J. Saßmannshausen, J. Klett, A. R. Kennedy, J. A. Parkinson and D. Armstrong, New J. Chem., 2013, 37, 494
    DOI: 10.1039/C2NJ40874K

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