Theoretical and experimental investigations of ligand exchange in guanidinate ligand systems for group 13 metals

• Published in: Dalton transactions : an international journal of inorganic chemistry no. 30; p. 3297
• Main Authors: Brazeau, Allison L, DiLabio, Gino A, Kreisel, Kevin A, Monillas, Wesley, Yap, Glenn P A, Barry, Seán T
• Format: Journal Article
• Language: English
• Published: England 14.08.2007
• ISSN: 1477-9226
• DOI: 10.1039/b706044k

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.