Theoretical and experimental investigations of ligand exchange in guanidinate ligand systems for group 13 metals |
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Authors: | Brazeau Allison L DiLabio Gino A Kreisel Kevin A Monillas Wesley Yap Glenn P A Barry Seán T |
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Affiliation: | Department of Chemistry, Carleton University, 1125 Colonel By Drive, Ottawa, Ontario, Canada. |
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Abstract: | The ligand exchange of guanidinate ligands between metal centres can play an important role in guanidinate chemistry, and ligand exchange between aluminium centres will form a dimeric intermediate. The synthesis and characterization of the dimer [Me(2)NC(N(i)Pr)(2)](2)Al(2)Cl(4) is reported here: compound crystallizes with a twisted boat conformation of its dimer ring. This compound decomposes to monomers at room temperature over four days, or within 18 hours at 90 degrees C. We undertook a detailed computational characterization of the reaction pathway, which supported the dimer structure and subsequent monomer formation. The ligand exchange route was also exploited for the synthesis of [MeC(N(i)Pr)(2)](2)AlCl, [EtC(N(i)Pr)(2)](2)AlCl, [MeC(N(i)Pr)(2)](2)GaCl, and [Me(2)NC(N(i)Pr)(2)](2)GaCl. |
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