Crystal and electronic structure of a hexacarbonyldiiron cluster tethered to naphthalene-2-thiolate ligands

Abstract

The structure of the previously reported complex bis(μ-naphthalene-2-thiolato-κ2 S:S)bis(tricarbonyliron)(Fe—Fe), [Fe2(C10H7S)2(CO)6], has been characterized by X-ray diffraction. In the solid state, the dinuclear complex adopts a butterfly-like shape, with an equatorial–axial spatial orientation of the naphthalene groups covalently coupled to the [S2Fe2(CO)6] unit. The asymmetric unit contains three independent [(μ-naphthalene-2-thiolato)2Fe2(CO)6] molecules. These molecules show intermolecular π–π stacking interactions between the naphthalene rings, which was confirmed by Hirshfield surface analysis. The electronic spectrum of the complex recorded in acetonitrile shows a band centered at 350 nm (∊ = 4.6 × 103 M −1 cm−1) and tailing into the visible region. This absorption can be attributed to a π→π* electronic transition within the naphthalene moiety and a metal-based d→d transition.