Metal-Induced C-N Bond Cleavage in the Decomposition of Alkali (R,R)-Bis(α-methylbenzyl)amide Complexes

Emily C. Border, Melissa Maguire, Jonathan G. Maclellan, Philip C. Andrews

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5 Citations (Scopus)


This study resulted in the isolation of new alkali metal complexes of (R,R)-bis(α-methylbenzyl)amine (B-α-mba) characterized by NMR spectroscopy and single-crystal X-ray diffraction where possible. The reaction outcome was found to be dependent on metal and Lewis donor choice to afford species [{PhCH(CH3)}2NLi·Dioxane]2 2, [{PhCH(CH3)}2NLi·HMPA]2 3, [{PhCH(CH3)}2NLi·TMEDA] 4, and [{PhCH(CH3)}2NNa·(THF)k]n 5 as simple amido species. Complex [{PhC(-CH2)}{PhCH(CH3)}NNa·TMEDA] 6 was isolated as a result of a β-hydride elimination. A complex mixture of species was isolated when B-α-mba was reacted with potassium in the presence of TMEDA and PMDETA to give species [{PhCH(CH3)}2NK·(TMEDA)k]n 7a, [{PhC(-CH2)}{PhCH(CH3)}NK·(TMEDA)k]n 7b, [{PhC(-CH2)NH}K·(TMEDA)k]n 7c, [{PhCH(CH3)}2NK·(PMDETA)k]n 8a, [{PhC(-CH2)}{PhCH(CH3)}NK·(PMDETA)k]n 8b, and [{PhC(-CH2)NH}K·(PMDETA)k]n 8c. In both cases, the decomposition to form the potassium enamide species 7c and 8c was the more favorable process. The decomposition reaction of B-α-mba with nBuNa in the presence of PMDETA to give the sodium enamide [PhC(-CH2)N(H)Na·PMDETA] 1 was investigated with GC-MS studies revealing the byproduct of this decomposition as styrene.

Original languageEnglish
Pages (from-to)1496-1504
Number of pages9
Issue number8
Publication statusPublished - 24 Apr 2017

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