In the pursuit of value-added products from the degradation of the abundant aromatic biopolymer lignin, homogeneous catalysis has the potential to provide a mild, selective route to monomeric phenols. Homogeneous vanadium catalysts have previously been shown to effectively cleave dimeric beta-O-4 model lignin compounds, with selectivity for C-C or C-O cleavage, or benzylic oxidation, depending on the ligand structure and oxidation state of the metal. In this study, a systematic kinetic investigation was undertaken in order to gain further understanding of the role of ligand structure and reaction conditions on the activity of vanadium Schiff-base catalysts towards a non-phenolic beta-O-4 model lignin dimer, and the selectivity of these species towards C-O bond cleavage. Catalytic activity was found to be increased by the addition of bulky, alkyl substituents at the 3'-position of the phenolate ring, whereas electron withdrawing substituents were found to dramatically reduce activity irrespective of their size. Selective depolymerization of a phenolic beta-O-4 dimer was also achieved. (C) 2015 Elsevier B.V. All rights reserved.