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Issue 4, 2001
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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

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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(PyNSiMe3)(12C4)] 2, in which the amide ligand binds through both the amido and pyridyl nitrogen centres. Metathesis of 2 with ButONa 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 = CH3CH2CH2CH2C(CH2CH3)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 CH3CH2CH2CH2C(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.

Graphical abstract: 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 [ ]

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Supplementary files

Article information


Submitted
03 Nov 2000
Accepted
22 Dec 2000
First published
29 Jan 2001

J. Chem. Soc., Dalton Trans., 2001, 402-408
Article type
Paper

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

S. T. Liddle and W. Clegg, J. Chem. Soc., Dalton Trans., 2001, 402
DOI: 10.1039/B008852H

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