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-κS:S)bis(tricarbonyliron)(Fe-Fe), [Fe(CHS)(CO)], 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 [SFe(CO)] unit. The asymmetric unit contains three independent [(μ-naphthalene-2-thiolato)Fe(CO)] 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 (ℇ = 4.6 × 10 M cm) 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.

Rational development of molecular earth-abundant metal complexes for electrocatalytic hydrogen production

“…The reorganization energies at different redox states are minimized so that the free energies of the catalytic intermediates are nearly the same, allowing catalytic HER to occur at nearly thermodynamic potentials [20]. Inspired by H2ases, a considerable number of metal catalysts based on Co , Ni , Fe [71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89], Cu [90][91][92], and Mo [93][94][95][96][97] have been developed for electro-and photocatalytic HER [98][99][100][101][102][103][104]. Catalytic systems utilizing metalloproteins or metallopolymers have also been reported for H2 production [81,[105][106][107][108][109][110][111][112].…”