Synthesis and reactivity of fac-[Fe(CO)(3)(SR)(3)](-) (R = C7H4SN, C4H3S, C4H2O-o-CH3) and heterotrimetallic Fe(II)-Ni(II)-Fe(II)-thiolate complex

The reaction of 2 equiv. of diorganyl disulfides, (bis(2-benzothiazolyl) di sulfide, di(2-thienyl) disulfide, and bis(2-methyl-3-furyl) disulfide), wit h 1 equiv. of [HFe(CO)(4)](-) affords the stable, tridentate fac-[Fe(CO)(3) (SR)(3)](-) (R = C7H4SN (1); C4H3S (2); C4H2O-o-CH3 (3)) via the formation of intermediate [RSFe(CO)(4)](-), respectively. In contrast, oxidative addi tion of 2-aminophenyl disulfide to [Fe(CO)(4)(-SC6H4-o-NH2)](-), obtained f rom reaction of [HFe(CO)(4)](-) and 2-aminophenyl disulfide, and concomitan t displacement Of [SC6H4-o-NH2](-) leads to the neutral monomeric compound cis-[Fe(CO)(2)(-SC6H4-o-NH2)(2)] (6). Obviously, the reactivity and stabili ty of the iron-thiolate derivatives may be tailored by pendant ligand selec tion, and the reaction pathway is tailored according to the bond strength i nherent in the organodisulfides and to the nucleophilicity of thiolate atom s in [RSFe(CO)(4)](-) complexes. In particular, compounds fac-[Fe(CO)(3)(SR )(3)](-) serve as chelating metalloligand and intermetal thiolate ligand-tr ansfer reagent to synthesize the linear heterotrinuclear [(CO)(3)Fe(mu -SR) (3)Ni(mu -SR)(3)Fe(CO)(3)] (4) (R = C4H2O-o-CH3) and the neutral [Fe(CO)(2) (SC4H3S)(2)(bipy)] (5) (bipy = bipyridine). (C) 2001 Elsevier Science B.V. All rights reserved.