Abstract
Equilibrium between Al atoms, trimethylaluminum (TMA), and an Al–TMA complex has been observed over the temperature range 341–396 K at 50 Torr total pressure. Rate constants for the forward reaction are reported from 296 to 396 K. A van't Hoff plot of the equilibrium constant versus 1/ T yields ΔH 0 and ΔS 0 values for the complexation reaction as −19.6 (±1.7) kcal mol −1 and −27.7 (±4.8) cal mol −1 K −1 , respectively. An MP2 calculation gives ΔH 0 of complexation as −12.6 kcal mol −1 . A complex which contains an Al–Al bond semi-bridged by a methyl group is predicted by ab initio and DFT calculations.
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