The interesting and somewhat unexpected solubilization of insoluble anhydrous divalent transition metal chlorides, MCl2 (M = Co, Ni and Cu) in benzene in the presence of Ti(OEt)(4) or Zr(OPri)(4) or Al(OPri)(3) in 1 : 2 and I : 4 molar ratios, followed by usual workup yields quantitatively, novel complexes of the general formulae MMx '(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-i) (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 = Pri) (8); M = Cu, M-' = Ti (x = 2, R = Et) (9); M = Cu, M-' = Ti (x = 4, R = Et) (10)] and CoAl2(OPri)(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.