Synthesis of new thiophenolato hydrido iron(II) complexes and their substitution reactions with alkynes

The novel thiophenolato hydrido iron(II) complexes [cis-Fe(H)(SAr)(PMe3)4] (4–6) (Ar = p-BrC6H4 (4), p-MeOC6H4 (5) and o-MeC6H4 (6)) were prepared through the reaction of Fe(PMe3)4 with thiophenols ArSH (1–3). Reaction of 6 with trimethylsilylacetylene and phenylacetylene afforded bisalkynyl iron(II) complexes [Fe(PMe3)4(CCSiMe3)2] (7) and [Fe(PMe3)4(CCPh)2] (9) through elimination of dihydrogen and the formation of thiophenol. The reaction of 5 with 2-methyl-3-butyn-2-ol gave [Fe(PMe3)4(CCCMe2OH)2] (10). The crystal structures of complexes 4, 7 and 10 were determined by X-ray diffraction. A mechanism for the formation of 7 is proposed.

[cis-Fe(H)(SAr)(PMe3)4] (4–6) were prepared by reaction of Fe(PMe3)4 with ArSH (1–3). Reaction of 6 with HCCSiMe3 and HCCPh afforded Fe(PMe3)4(CCSiMe3)2 (7) and Fe(PMe3)4(CCPh)2 (9). Reaction of 5 with HCCCMe2OH afforded Fe(PMe3)4(CCCMe2OH)2 (10). Crystal structures of 4, 7 and 10 were determined. The formation mechanism of 7 is discussed.Figure optionsDownload as PowerPoint slide