Synthesis, structure and solution studies on mixed aryl/alkyl lithium zincates

Roberts, Andrew J. and Kennedy, Alan R. and McLellan, Ross and Robertson, Stuart D. and Hevia, Eva (2016) Synthesis, structure and solution studies on mixed aryl/alkyl lithium zincates. European Journal of Inorganic Chemistry. pp. 4752-4760. ISSN 1434-1948

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    Abstract

    Novel homo- and heteroleptic lithium zincates have been prepared by cocomplexation reactions of Zn(CH2SiMe3)2 and PhLi in low-polarity hydrocarbon solvents. X-ray crystallographic studies of products obtained by reacting the organometallic reagents in benzene or toluene yield the novel solvent-free solid-state arrangement [Li4Zn3Ph5(CH2SiMe3)5]⋡ (1). Combining Zn(CH2SiMe3)2 and PhLi in hexane in the presence of the polydentate N-donors PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) or TMEDA (N,N,N′,N′-tetramethylethylenediamine) reveals monomeric heteroleptic [(PMDETA)LiZn(CH2SiMe3)2Ph] (2) and homoleptic [(TMEDA)LiZn(CH2SiMe3)3] (3), the result of a disproportionation process, respectively. NMR spectroscopic studies suggest that 2 and 3 retain their discrete contacted ion-pair solid-state structures in benzene solution. Variable-temperature NMR spectroscopic studies of 2 in [D8]THF reveal a complex equilibrium also including [LiZn(CH2SiMe3)3], [LiZn(CH2SiMe3)Ph2] and [LiZnPh3], an equilibrium process analogous to that of 1 in THF. This study further highlights the complexity of these reactions, which at first would appear simple.

    Creators(s): Roberts, Andrew J. ORCID logoORCID: https://orcid.org/0000-0001-7642-4393, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, McLellan, Ross ORCID logoORCID: https://orcid.org/0000-0001-9700-0258, Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770 and Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506;
    Item type:Article
    ID code:58482
    Notes:The version posted must include a notice on the first page as follows: "This is the peer reviewed version of the following article: Roberts, A. J., Kennedy, A. R., McLellan, R., Robertson, S. D., & Hevia, E. (2016). Synthesis, structure and solution studies on mixed aryl/alkyl lithium zincates. European Journal of Inorganic Chemistry, 4752-4760. DOI: 10.1002/ejic.201601020, which has been published in final form at http://dx.doi.org/10.1002/ejic.201601020. This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving".
    Keywords:zincates, lithium, solvent effects, bimetallic chemistry, cocomplexation, Chemistry, Chemistry(all)
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:04 Nov 2016 12:27
    Last modified:20 Feb 2020 04:22
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/58482
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