Ligand L exchange and the aryl rotation of BDI ligand of the title complexes have been examined in the solution of toluene-d8, CD2Cl2, THF-d8, and pyridine-d5 by dynamic 1H and 13C{1H} NMR lineshape analyses. The results suggest that theses aryl rotation and ligand L exchange of all complexes are coupled. The rate of ligand L exchange increases in the order of DMAP, py, THF, and 2-MeTHF, respectively. Evidence is presented that the ligand L exchange undergoes both dissociative and associative processes. At low concentrations of added L, the dissociative process is predominant while the associative process is kinetically favorable in high concentrations of L. When L =THF, the activation of enthalpy (?H?) and entropy (?S?) are 13.5 � 0.6 kcal mol-1 and 9.6 � 2.3 cal mol-1K-1 for dissociative process, and 4.7 � 0.1 kcal mol-1  and = -25.7 � 0.6 cal mol-1 K-1 for associative process, respectively.

Dynamic exchange processes involving BDIMgBu<i><sup>n</sup></i>(L) complexes, BDI = β-diiminato ligand, L = THF, 2-MeTHF, py and DMAP

245th National Meeting (2013)

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Dynamic exchange processes involving BDIMgBun(L) complexes, BDI = β-diiminato ligand, L = THF, 2-MeTHF, py and DMAP

Dynamic exchange processes involving BDIMgBuⁿ(L) complexes, BDI = β-diiminato ligand, L = THF, 2-MeTHF, py and DMAP