Elsayed Moussa Mehdi, Seidl Michael, Balázs Gábor, Hautmann Matthias, Scheer Manfred
Institute für Anorganische Chemie der, Universität Regensburg, 93040, Regensburg, Germany.
Angew Chem Int Ed Engl. 2019 Sep 9;58(37):12903-12907. doi: 10.1002/anie.201907067. Epub 2019 Aug 19.
The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp Mo (CO) (μ,η :η -PE)] (Cp=C H ; E=As (1), Sb (2)), with Cu halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo PE units and the Cu halide, the oligomers [⟨{Cp Mo (CO) }{μ ,η :η :η :η -PE}⟩ ⟨{CuX}{Cu(μ-X)}⟩ ] (E=As (X=Cl (3), Br (4)); E=Sb (X=Cl (6), Br (7))) or the 1D coordination polymers [{Cp Mo (CO) }{μ ,η :η :η :η -PAs}{Cu(μ-I)}] (5) and [{Cp Mo (CO) }{μ ,η :η :η :η -PSb} {Cu(μ-X)} ] (X=I (8), Br (9)) are accessible. These solid-state aggregates are the first and only examples featuring the organometallic heterodiatomic Mo PE complexes 1 and 2 as linking moieties. DFT calculations demonstrate that complexes 1 and 2 present a unique class of mixed-donor ligands coordinating to Cu centers via the P lone pair and the P-E σ-bond, revealing an unprecedented coordination mode.
带有未取代的第15族异双原子元素的四面体钼配合物[CpMo(CO)(μ,η²:η² -PE)]（Cp = C₅H₅；E = As（1），Sb（2））与卤化铜反应得到了七种前所未有的中性超分子组装体。根据Mo-PE单元和卤化铜的不同，可得到低聚物[⟨{CpMo(CO)}₂{μ,η²:η²:η²:η² -PE}⟩⟨{CuX}{Cu(μ -X)}⟩]（E = As（X = Cl（3），Br（4））；E = Sb（X = Cl（6），Br（7）））或一维配位聚合物[{CpMo(CO)}₂{μ,η²:η²:η²:η² -PAs}{Cu(μ -I)}]（5）和[{CpMo(CO)}₂{μ,η²:η²:η²:η² -PSb}{Cu(μ -X)}]（X = I（8），Br（9））。这些固态聚集体是以有机金属异双原子Mo-PE配合物1和2作为连接部分的首个也是唯一的例子。密度泛函理论计算表明，配合物1和2呈现出一类独特的混合供体配体，它们通过P孤对电子和P-E σ键与铜中心配位，揭示了一种前所未有的配位模式。
