Technetium(V) and rhenium(V) complexes with N-(2-mercaptophenyl)salicylideneiminate. Crystal structure of chloro(oxo)[N-(2-sulphidophenyl)salicylideneiminato-NOS]technetium(V)

The reactions of the tridentate Schiff-base ligand derived from salicylaldehyde and o-aminothio-phenol (H2L1) with [MOCl4]- (M = Tc or Re) have been investigated. The complexes [MOCl(L1)], [ReOCl2(L1)]-, and [ReOCl(X) (L1)] (X = MeOH or EtOH) were synthesized and characterized by elemental analysis, i.r., 1H n.m.r., and u.v.-visible spectroscopy, mass spectrometry, magnetic susceptibility, conductivity, and thermogravimetric measurements and the complete configurations of the complexes were determined. X-Ray crystallographic investigation on [TcOCl(L1)] shows the molecular structure to be a distorted square pyramid having the ligand L1 in the equatorial plane with respect to Tc=O. The molecule is in the monoclinic space group P21/a, with a = 14.255(9) b = 12.495(7), c = 7.865(6) Å, ? = 105.22(5)°, and Z = 4. The structure has been refined to R = 0.068 for 2 184 observed reflections. The reactions of [MOCl(L1)] (M = Tc or Re) or [ReOCl(X)(L1)] (X = MeOH or EtOH) with the bidentate Schiff-base ligands (HL) salicylideneimine (HL3), N-methylsalicylideneimine (HL4), N-phenylsalicylidene-imine (HL5), N-(2-hydroxyphenyl)-p-nitrobenzylideneimine (HL6), quinolin-8-ol (Hquin), quinoline-8-thiol (Htquin), and N-(2-mercaptophenyl)-p-nitrobenzylideneimine (HL7) lead to the 'mixed' compounds [MO(L1)(L)]. The products with L = tquin or L7 were obtained only for [ReOCl(X)(L1)] (X = MeOH or EtOH). All these complexes were characterized by the physicochemical techniques listed above.