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Addition of Aluminum and Gallium Species to Aromatic and Alkyl-Substituted 1,4-Diaza-1,3-butadiene Ligands

By Ana M. Felix (2092843), Diane A. Dickie (1716490), Ian S. Horne (2092846), Giang Page (2092840) and Richard A. Kemp (1469038)


In this report, we investigate the interactions of Me<sub><i>x</i></sub>MCl<sub>3–<i>x</i></sub> (<i>x</i> = 0–3, M = Al, Ga) with various aromatic and alkyl-substituted 1,4-diaza-1,3-butadiene <sup>R</sup>DAB ligands (or α-diimine ligands) to give a variety of structures in solution and in the solid state. In combination with other previously reported structures, certain general trends of reactivity of these species can be deduced, although there are still some unexplained modes of reactivity. The methylated Al species react with aromatic-substituted <sup>R</sup>DAB ligands to provide final products that result from CN insertion into the Al–CH<sub>3</sub> group followed by rearrangement reactions. The addition of methyl groups onto the backbone of the <sup>R</sup>DAB ligand is insufficient to stop the insertion and rearrangement processes from occurring. In the case of MeAlCl<sub>2</sub> with the bulky <sup>DiPP</sup>DAB ligand, the reaction could be followed spectroscopically from the monoadduct through the inserted/rearranged final product. Methylated Ga species, however, are much less predictable in their behavior with aromatic-substituted <sup>R</sup>DAB ligands. Depending on the exact species and ratios used, coordinated adducts can be formed and identified, or inserted/rearranged products similar to the aluminum reactions can be obtained. Quite interestingly, cation/anion pairs can also be formed in which GaCl<sub>3</sub> or MeGaCl<sub>2</sub> act as a chloride acceptors. This behavior was unique and substantially different from the analogous Al reactions which formed either a dicoordinated adduct or an inserted/rearranged complex. When the stronger-donating alkyl-substituted <sup>R</sup>DAB ligands were used with Me<sub>2</sub>GaCl, only cation/anion pairs were obtained. Surprisingly, when the same reactions were performed using Me<sub>2</sub>AlCl as a reagent, irreproducible results were obtained

Topics: Biochemistry, Molecular Biology, Pharmacology, Biotechnology, Developmental Biology, Infectious Diseases, Plant Biology, Computational Biology, Chemical Sciences not elsewhere classified, dicoordinated adduct, Al reactions, DiPPDAB ligand, aluminum reactions, chloride acceptors, methyl groups, Gallium Species, MeAlCl 2, rearrangement processes, methylated Al species, RDAB ligand, MeGaCl 2 act, Methylated Ga species, rearrangement reactions, GaCl 3, irreproducible results
Year: 2012
DOI identifier: 10.1021/ic202583w.s001
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