The interesting and somewhat unexpected solubilization of insoluble anhydrous divalent transition metal chlorides, MCl 2 (M = Co, Ni and Cu) in benzene in the presence of Ti(OEt) 4 or Zr(OPr i ) 4 or Al(OPr i ) 3 in 1 : 2 and 1 : 4 molar ratios, followed by usual workup yields quantitatively, novel complexes of the general formulae MM' x (OR) 4x Cl 2 [where M = Co, M' = Ti (x = 2, R = Et) (1); M = Co, M' = Ti (x = 4, R = Et) (2); M = Co, M' = Zr (x = 2, R = Pr i ) (3); M = Co, M' = Zr (x = 4, R = Pr') (4); M = Ni, M' = Ti (x = 2, R = Et) (5); M = Ni, M' = Ti (x = 4, R = Et) (6); M = Ni, M' = Zr (x = 2, R = Pr i ) (7); M = Ni, M' = Zr (x = 4, R = Pr i ) (8); M = Cu, M' = Ti (x = 2, R = Et) (9); M = Cu, M' = Ti (x = 4, R = Et) (10)] and CoAl 2 (OPr i ) 6 Cl 2 (11). All of these complexes are highly moisture-sensitive coloured solids, soluble in typical organic solvents and have been successfully characterized by elemental analysis, spectroscopic and magnetic studies as well as by molecular weight measurements.