Andrikopoulos, P.C. and Armstrong, D.R. and Barley, H.R.L. and Clegg, W. and Dale, S.H. and Hevia, E. and Honeyman, G.W. and Kennedy, A.R. and Mulvey, R.E. (2005) Sodium dialkyl-amidozincates: Alkyl or amido bases? An experimental and theoretical case study. Journal of the American Chemical Society, 127 (17). pp. 6184-6185. ISSN 0002-7863Full text not available in this repository. (Request a copy from the Strathclyde author)
Alkali metal zincate reagents are attracting considerable attention at present in respect to their often special reactivity/selectivity in hydrogen-metal and halogen-metal interconversion reactions. Heteroleptic diorgano-amidozincates, typified by lithium di-tert-butyltetramethylpiperidinozincate, have proved to be especially useful reagents in such applications. In this paper the related sodium TMP-zincate, prepared as its TMEDA (N,N,N',N'-tetramethylethylenediamine) adduct, [TMEDA·Na(-tBu)(-TMP)Zn(tBu)], 1, is introduced. This new zincate was synthesized from a 1:1:1 mixture of tBu2Zn, NaTMP, and TMEDA in hexane solution, as a colorless crystalline solid in an isolated yield of 58%. It has been characterized in solution by 1H and 13C NMR spectroscopic studies. An X-ray crystallographic study reveals that 1 adopts a five-membered (NaNZnCC) ring system featuring a TMP bridge and an unusual, asymmetrical tBu bridge involving a Na···Me agostic contact. Probing the basicity of 1, reaction with benzene affords the new hetero(tri)leptic zincate [TMEDA·Na(-Ph)(-TMP)Zn(tBu)], 2, which has also been crystallographically characterized. Thus, in this hydrogen-metal exchange reaction 1 functions as an alkyl base, with the elimination of butane, as opposed to an amido base. Also reported are DFT calculations using B3LYP functionals and the 6-311G** basis set on model zincate systems, which intimate that the preference of 1 for tBu ligand transfer over TMP ligand transfer in the reaction toward benzene is due to favorable thermodynamic factors.
|Keywords:||macrocyclic amide, inverse crowns, ate complexes, chemistry, selectivity, magnesium, Chemistry, Biochemistry, Colloid and Surface Chemistry, Chemistry(all), Catalysis|
|Subjects:||Science > Chemistry|
|Department:||Faculty of Science > Pure and Applied Chemistry|
|Depositing user:||Mr Derek Boyle|
|Date Deposited:||28 Mar 2006|
|Last modified:||06 Jan 2017 03:45|