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Cation-induced structural variations in the alkali metal derivatives of 2-trimethylsilylaminopyridine: Synthesis and X-ray structures of complexes for all five metals Li-Cs with 12-crown-4

Lookup NU author(s): Dr Stephen Liddle, Professor William Clegg

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Abstract

The secondary amine 2-trimethylsilylaminopyridine [PyN(H)SiMe3] 1 was synthesised by mono-lithiation of 2-aminopyridine and subsequent reaction with Me3SiCl. The compound is readily metallated by BunLi in ethereal solvent, in the presence of the macrocyclic polyether 12-crown-4 (12C4), to afford the lithium secondary amide complex [Li(PyNSiMe 3)(12C4)] 2, in which the amide ligand binds through both the amido and pyridyl nitrogen centres. Metathesis of 2 with ButO Na yields the unusual 'ate' solvent-separated ion pair complex [Na(12C4)2]- [Na(PyNSiMe3)2(THF)]·(THF) 3. Metathesis of 2 with ROM [R = But, M = K; R = CH3CH2CH 2CH2C(CH2-CH3)HCH2, M = Rb] yields the two bridged dimers [{K(PyNSiMe3)(12C4)} 2]·2PhMe 4 and [{Rb(PyNSiMe3)-(12C4)}2] 5. In both 4 and 5 the amido and pyridyl nitrogens bridge between metal centres. Room temperature metathesis of 2 with CH3CH2CH 2CH2C(CH2CH3)HCH2OCs yields the polymeric [{Cs(PyNH)(12C4)}∞] 6 containing tetranuclear cluster units, with concomitant cleavage of the N-Si bond. Such cleavage is prevented by low temperature synthesis, yielding the bridged dimer complex [{Cs(PyNSiMe3)(12C4)}2]·PhMe 7. The compounds have been characterised by multinuclear NMR spectroscopy, CHN microanalysis and (for 2.7) X-ray crystallography. © The Royal Society of Chemistry 2001.

Publication metadata

Author(s): Liddle ST, Clegg W

Publication type: Article

Publication status: Published

Journal: Journal of the Chemical Society, Dalton Transactions

Year: 2001

Volume: 2001

Issue: 4

Pages: 402-408

ISSN (print): 1470479X

ISSN (electronic):

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/B008852H

DOI: 10.1039/B008852H

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