UEBERGANGSMETALL-KOMPLEXE MIT SCHWEFELLIGANDEN. XXI. THIOLATO-AMIN-KOMPLEXE VON EISEN(II) UND MOLYBDAEN(II) MIT -EINHEITEN UND CO-, PMe3-, NO- SOWIE N2H4-KOLIGANDEN (SNNS=(SC6H4N(R)C2H4N(R)C6H4S)(2-), R=H, CH3)

Article abstract of DOI:10.1016/0022-328X(86)80354-0

Iron(II) and molybdenum(II) complexes with the tetradentate thiolate amine ligands bmae(2-) and bmab(2-) respectively have been synthesized in order to compare their properties with the isoelectronic complexes containing the tetradentate thiolate-thioether ligand dttd(2-) .The reaction of FeCl2*4H2O with bmae-Na2 and CO in MeOH at ambient temperatures yields ; by analogous procedures , and are obtained.Heating as well as UV irradiation of in solution lead to reversible CO elimination and the formation of respectively; in the presence of PMe3, the complex forms.The same reactions are observed with the complexes.The coordinatively unsaturated is accessible by several methods, for example by the facile NaBH4 reduction of the Schiff base complex , ; from the free ligand bmae-H2 is obtained by hydrolysis with NaOH/DMF or HCl/THF.Although is only poorly soluble in all common solvents, suspensions of it react rapidly with CO and PMe3 yielding the corresponding complexes.With N2H4 and NO respectively and the paramagnetic (μ_eff 1.71 B.M.) are obtained.In contrast to the reduction labile fragment the unit is stable even against strongly reducing agents e.g.Na in liquid ammonia.Until now only was obtained as an example of a low oxidation state complex, from the reaction of with bmae-Na2.All compounds were characterized spectroscopically as well as by elemental analysis.