Theoretical and experimental investigations of ligand exchange in guanidinate ligand systems for group 13 metals.
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.
Brazeau
Allison L
AL
Department of Chemistry, Carleton University, 1125 Colonel By Drive, Ottawa, Ontario, Canada.
DiLabio
Gino A
GA
Kreisel
Kevin A
KA
Monillas
Wesley
W
Yap
Glenn P A
GP
Barry
Seán T
ST