Issue 2, 2013

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

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

Supplementary files

Additions and corrections

Article information

Article type
Paper
Submitted
27 Sep 2012
Accepted
17 Nov 2012
First published
19 Nov 2012

New J. Chem., 2013,37, 494-501

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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