A series of trans-dicyanide vanadium(III) compounds based on acetylacetonate, (PPN)[V-III(acac)(2)(CN)(2)]center dot(PPN)Cl center dot 2MeCN (1), and salen ligands, (Et4N)[V-III(salen)(CN)(2)] (2a), (PPN)[V-III(MeOsalen)(CN)(2)]center dot DMF center dot 2MeCN (3), and (PPN)[V-III(salphen)(CN)(2)]center dot DMF (4) [salen = N,N '-ethylenebis(salicyl-imine), MeOsalen = N,N '-ethylenebis(methoxysalicylimine), salphen = N,N '-phenylenebis(salicyl-imine), and PPN = bis(triphenylphosphine)iminium], were prepared and structurally characterized. High-field EPR studies reveal that the complexes exhibit moderate magnetic anisotropy with positive D values of +5.70, +3.80, +4.05, and +3.99 cm(-1) for 1-4, respectively.