Crystal and electronic structure of a hexacarbonyldiiron cluster tethered to naphthalene‐2‐thiolate ligands. Issue 2 (23rd January 2018)

• Record Type: Journal Article
• Authors: Mebi, Charles; Gerasimchuk, Nikolay; Labrecque, Jordan
• Is Part Of: Acta crystallographica. Volume 74:Issue 2(2018)
• Page Start: 224
• Page End: 228
• Publication Date: 2018-01-23
• Subjects: cluster compound -- diiron(II) compound -- hydrogenase model -- crystal structure -- naphthalene‐2‐thiolate -- iron carbonyl -- Hirshfield surface analysis -- electronic spectrum -- electrochemical reduction; Crystallography -- Periodicals; Crystals -- Periodicals; 548.3
• DOI: 10.1107/S2053229618000712
• Languages: English
• ISSNs: 2053-2296

Abstract

Abstract : The molecular structure of [(μ‐naphthalene‐2‐thiolato)2 Fe2 (CO)6 ], determined by X‐ray diffraction, displays intermolecular π–π stacking interactions between the naphthalene rings, which was confirmed by Hirshfield surface analysis. The electronic spectrum shows a band which can be attributed to a π→π* electronic transition within the naphthalene moiety and a metal‐based d → d transition. Abstract : The structure of the previously reported complex bis(μ‐naphthalene‐2‐thiolato‐κ 2 S : S )bis(tricarbonyliron)( Fe — Fe ), [Fe2 (C10 H7 S)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 [S2 Fe2 (CO)6 ] unit. The asymmetric unit contains three independent [(μ‐naphthalene‐2‐thiolato)2 Fe2 (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 (ϵ = 4.6 × 10 3 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.