Abstract
Evidence of the existence of correlated intramolecular orientation (gear effect) has been observed in Pri2NNO (1) and Pri2NNNPh (2) by 13C n.m.r. In the first case two conformers have been detected in a 92 :8 ratio at –120 °C. The corresponding activation parameters have been measured (ΔG‡ 9.7 kcal mol–1) and the structures of the two conformers assigned. Molecular mechanics calculations reproduce all the experimental observations and indicate, in addition, that this dynamic process is not synchronous but follows a two-step pathway. In the case of (2) the existence of the phenomenon could be detected through the interpretation of the selective broadening of one spectral line, and the free energy of activation could be measured (ΔG‡ 10.2 kcal mol–1) even though the spectrum of the less populated conformer was not directly detected.
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Schedule a callMore From: Journal of the Chemical Society, Perkin Transactions 2
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