The effect of ligand substitution on bonding to other ligands has been investigated in a series of V(III) complexes. Nuclear magnetic resonance (n.m.r.) contact shifts have been utilized for this purpose. These shifts are interpreted as arising from metal to ligand charge transfer. The results obtained are contrary to those expected from simple considerations of the electron withdrawing or donating abilities of the substituents. Electron withdrawing substituents decrease the charge transfer to the substituted ligand and increase the charge transfer to the remaining ligands. Electron donating substituents have the opposite effect. A simple interpretation is proposed to account for these results. An electron withdrawing substituent on a ligand in thexyplane increases the occupancy of dxywhich cannot interact with the π system of the ligand in thexyplane but which is available for π bonding with the remaining ligands. Effects of this type are to be anticipated whenever the filling of thet2gorbitals is not symmetrical.