McNeil Derek L, Beckford Daihlia J, Kneebone Jared L, Carpenter Stephanie H, Brennessel William W, Neidig Michael L
Department of Chemistry, University of Rochester, Rochester, NY 14627, USA.
Acta Crystallogr E Crystallogr Commun. 2018 May 15;74(Pt 6):803-807. doi: 10.1107/S2056989018006898. eCollection 2018 Jun 1.
Structural characterization of the ionic complexes [FeCl(CHP)][FeCl]·0.59CHCl or [(dppen)FeCl][FeCl]·0.59CHCl (dppen = -1,2-bis-(di-phenyl-phosphane)ethyl-ene, PCH) and [FeCl(CHP)][FeCl]·CHCl or [(dpbz)FeCl][FeCl]·CHCl (dpbz = 1,2-bis-(di-phenyl-phosphane)benzene, PCH) demonstrates coordination of two bidentate phosphane ligands (bis-phosphanes) to a single iron(III) center, resulting in six-coordinate cationic complexes that are balanced in charge by tetra-chlorido-ferrate(III) monoanions. The bis-phosphane coordination is consistent will all previously reported mol-ecular structures of six coordinate iron(III) complex cations with a (PP) ( = halido) donor set. The complex with dppen crystallizes in the centrosymmetric space group 2/ as a partial-occupancy [0.592 (4)] di-chloro-methane solvate, while the dpbz-ligated complex crystallizes in the triclinic space group 1 as a full di-chloro-methane monosolvate. Furthermore, the crystal studied of [(dpbz)FeCl][FeCl]·CHCl was an inversion twin, whose component mass ratio refined to 0.76 (3):0.24 (3). Beyond a few very weak C-H⋯Cl and C-H⋯π inter-actions, there are no significant supra-molecular features in either structure.
离子配合物[FeCl(CHP)][FeCl]·0.59CHCl或[(dppen)FeCl][FeCl]·0.59CHCl（dppen = -1,2-双（二苯基膦基）乙烯，PCH）以及[FeCl(CHP)][FeCl]·CHCl或[(dpbz)FeCl][FeCl]·CHCl（dpbz = 1,2-双（二苯基膦基）苯，PCH）的结构表征表明，两个双齿膦配体（双膦）与单个铁（III）中心配位，形成六配位阳离子配合物，其电荷由四氯合铁（III）单阴离子平衡。双膦配位与之前报道的所有具有(PP)（ = 卤化物）供体集的六配位铁（III）配合物阳离子的分子结构一致。与dppen形成的配合物以中心对称空间群2/结晶，为部分占据[0.592 (4)]的二氯甲烷溶剂化物，而与dpbz配位的配合物以三斜空间群1结晶，为全二氯甲烷单溶剂化物。此外，研究的[(dpbz)FeCl][FeCl]·CHCl晶体是一个倒反孪晶，其组分质量比精修为0.76 (3):0.24 (3)。除了一些非常弱的C-H⋯Cl和C-H⋯π相互作用外，两种结构中均没有显著的超分子特征。
