S. Liddle, W. Clegg
2001
Citations
0
Influential Citations
26
Citations
Journal
Journal of The Chemical Society-dalton Transactions
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.