How bulky is a bulky ligand: energetic consequences of steric constraint in ligand-directed cluster assembly and disassembly.
Steric tuning of N-aryl groups of homologous amidinate ligands affords discrete dimeric and tetrameric copper(I) clusters in solid state, but they undergo dynamic dimer-dimer and tetramer-dimer interconversion in solution. A delicate interplay between steric constraint and mechanical stability shapes the reaction coordinate of this process. Thermodynamic and kinetic parameters dictating such cluster assembly and disassembly immediately suggest a means to experimentally quantify energies that are associated with ligand steric bulk.
Jiang
Xuan
X
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.
Bollinger
John C
JC
Lee
Dongwhan
D