Reactivity of MOCl(L) (M = Tc or Re; L = N-(2-oxidophenyl)salicylideneiminate or N-(2-sulphidophenyl)salicylideneiminate) with tertiary phosphines. X-ray molecular structure of ?-oxo-bis[(N-(2-oxidophenyl)salicylideneiminato(2-)NOO?)bis(dimethylphenylphosphine)technetium(III)]

?-O[Tc(L)(P)2]2 and ReOCl(L)(P) complexes (L = N-(2-oxidophenyl)salicylideneiminate (L1) or N-(2-sulphidophenyl)salicylideneiminate (L2) and P = PMe2Ph or PPh3) were synthesized starting from the MOCl(L) (M = Tc or Re) compounds. The characterization was performed by means of the usual physicochemical techniques and for ?-O[Tc(L1)(PMe2Ph)2]2 by means of X-ray structure determination. In the complex the coordination around each technetium atom is approximately octahedral with two phosphine ligands in the trans position and the remaining four equatorial sites occupied by ONO donor atom set of L1 ligand and the bridge-oxo oxygen. Consequently the oxo oxygen is trans to the imino nitrogen of the L1 ligand. The complex crystallizes in triclinic space group P1 with a = 16.709(7), b = 15.255(6), c = 11.702(4) Å, ? = 104.43(5), ? = 86.49(6), ? = 106.91(6)°, U = 2763.6(1.8) Å3, Z = 2. The structure has been refined to R = 0.08 for 2311 independent reflections.