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Issue 26, 2008
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Synthesis and structures of crystalline Li, Al and Sn(II) 1-azaallyls and β-diketiminates derived from [Li{μ,η3-N(SiMe3)C(Ad)C(H)SiMe3}]2 (Ad = 1-adamantyl)

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Abstract

The crystalline dimeric 1-azaallyllithium complex [Li{μ,η3-N(SiMe3)C(Ad)C(H)SiMe3}]2 (1) was prepared from equivalent portions of Li[CH(SiMe3)2] and 1-cyanoadamantane (AdCN). Complex 1 was used as precursor to each of the crystalline complexes 2–8 which were obtained in good yield. By 1-azaallyl ligand transfer, 1 afforded (i) [Al{η3-N(SiMe3)C(Ad)C(H)SiMe3}{κ1-N(SiMe3)C(Ad)[double bond, length as m-dash]C(H)SiMe3-E}Me] (5) with [AlCl2Me]2, (ii) [Sn{η3-N(SiMe3)C(Ad)C(H)SiMe3}2] (7) with Sn[N(SiMe3)2]2, and (iii) [Li(N{C(Ad)[double bond, length as m-dash]C(H)SiMe3-E}{Si(NN)SiMe3})(thf)2] (8) with the silylene Si[(NCH2But)2C6H4-1,2] [= Si(NN)]. By insertion into the C[triple bond, length as m-dash]N bond of the appropriate cyanoarene RCN, 1 gave the β-diketiminate [Li{μ-N(SiMe3)C(Ad)C(H)C(R)NSiMe3}]2 [R = Ph (2), C6H4Me-4 (3)], and 5 yielded [Al{κ2-N(SiMe3)C(Ad)C(H)C(Ph)NSiMe3}{κ1-N(SiMe3)C(Ad)[double bond, length as m-dash]C(H)SiMe3-E}Me] (6). The β-diketiminate [Al{κ2-N(SiMe3)C(Ad)C(H)C(Ph)NSiMe3}Me2] (4) was prepared from 2 and [AlClMe2]2. The X-ray structures of 1 and 3–8 are presented. Multinuclear NMR spectra in C6D6 or C6D5CD3 have been recorded for each of 1–8; such data on 8 revealed that in solution two minor isomers were also present.

Graphical abstract: Synthesis and structures of crystalline Li, Al and Sn(ii) 1-azaallyls and β-diketiminates derived from [Li{μ,η3-N(SiMe3)C(Ad)C(H)SiMe3}]2 (Ad = 1-adamantyl)

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Publication details

The article was received on 04 Dec 2007, accepted on 31 Jan 2008 and first published on 11 Mar 2008


Article type: Paper
DOI: 10.1039/B718728A
Dalton Trans., 2008, 3493-3501

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    Synthesis and structures of crystalline Li, Al and Sn(II) 1-azaallyls and β-diketiminates derived from [Li{μ,η3-N(SiMe3)C(Ad)C(H)SiMe3}]2 (Ad = 1-adamantyl)

    L. Bourget-Merle, P. B. Hitchcock, M. F. Lappert and P. G. Merle, Dalton Trans., 2008, 3493
    DOI: 10.1039/B718728A

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