James J. Harrison

Mechanism of thermolysis of tetramethylammonium μ-chlorobis(triethylaluminate)

Abstract The thermolysis of tetramethylammonium μ-chlorobis(triethylaluminate) has been investigated. In addition to the previously reported products, [Me4N][Clue5f8AlEt3] and (AlEt3)2, Me3N · AlEt3 is formed simultaneously in lesser amounts. A mechanism for the observed thermolysis reactions is presented which predicts formation of methyl chloride as a transient species which undergoes further reaction with (AlEt3)2 to ultimately produce methane and ethylene. The experimentally observed methane/ethylene ratio supports the proposed mechanism.

Dissociative Phenomena in Triethylaluminum Complexes of Alkali Metal Halides and Pseudohalides

Abstract During the course of investigations into the stability of complexes derived from triethylaluminum and alkali metal halides and pseudohalides, we have discovered that 1–decene induces dissociation of A1Et3 from M[A12Et6X] complexes, where MX = KC1, KN3, NaN3, KSCN, NaCN and NaF. These results provide experimental evidence that an olefin-alkylaluminum π interaction can be sufficiently strong to promote cleavage of the A1−X sigma bond, X = halide or pseudohalide in these systems.