Reaction of VO(acac)2 (Hacac = pentane-I ,4-dione) or VCI3 with ethanolic solutions containing excess of sodium ethane-I ,Z-dithiolate (Na,edt) yields deep green and deep red solutions, respectively, from which the complexes "Me,] Na[VO(edt),] -2EtOH (1) and [Ph,P],[V,(edt),](2) have been isolated and structurally characterized; e.s.r. data for (1) are included.1 Quoted g values are corrected for second-order shifts.