Bischalcogenides and transition metal complexes of cyclodiphosphazane derived diphosphaferrocenophane

Abstract

Oxidation reactions and transition metal chemistry of diphosphaferrocenophane [Fe(η5-C5H4)2(μ-PNtBu)2] (1) has been reported. The reactions of 1 with aq. H2O2 and elemental selenium afforded bis-chalcogenides, [Fe(η5-C5H4)2(μ-P(E)NtBu)2] (E=O; 2, E=Se; 3). Treatment of 1 with [Rh(COD)Cl]2 and [Pd(η3-C3H5)Cl]2 in 1:1 molar ratio afforded binuclear complexes, [{RhCl(COD)}2{Fe(η5-C5H4)2(μ-PNtBu)2}] (4) and [{Pd(η3-C3H5)Cl}2{Fe(η5-C5H4)2(μ-PNtBu)2}] (5), respectively. The mixed-ligand binuclear CuI complex [{(2,2′-bpy)CuI}2{Fe(η5-C5H4)2(μ-PNtBu)2}] (6) was synthesized by the reaction of 1 with CuI followed by treatment with 2,2′-bipyridine. The reaction between 1 and [AuCl(SMe2)] in 1:2 molar ratio yielded the dinuclear complex [(AuCl)2{Fe(η5-C5H4)2(μ-PNtBu)2}] (7) showing intermolecular aurophilic interactions in the crystal lattice. The crystal structures of 2, 4–7 were established by single-crystal X-ray diffraction studies.