Weller Ruth, Müller Igor, Duhayon Carine, Sabo-Etienne Sylviane, Bontemps Sébastien, Werncke C Gunnar
Department of Chemistry, Philipps-University Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, Germany.
Dalton Trans. 2021 Apr 14;50(14):4890-4903. doi: 10.1039/d1dt00121c. Epub 2021 Mar 22.
The synthesis and characterization of neutral quasilinear 3d-metal(i) complexes of chromium to cobalt of the type [KM(N(Dipp)SiMe)] (Dipp = 2,6-di-iso-propylphenyl) are reported. In solid state these metal(i) complexes either occur as isolated molecules (Co) or are part of a potassium ion linked 1D-coordination polymer (Cr-Fe). In solution the potassium cation is either ligated within the ligand sphere of the metal silylamide or is separated from the complex depending on the solvent. For iron, we showcase that it is possible to use sodium or lithium metal for the reduction of the metal(ii) precursor. However, in these cases the resulting iron(i) complexes can only be isolated upon cation separation using an appropriate crown-ether. Further, the neutral metal(i) complexes are used to introduce NBu as an organic cation in the case of cobalt and iron. The impact of the intramolecular cation complexation was further demonstrated upon reaction with diphenyl acetylene which leads to bond formation processes and redox disproportionation instead of η-alkyne complex formation.
报道了类型为[KM(N(Dipp)SiMe)]（Dipp = 2,6 - 二异丙基苯基）的铬到钴的中性准线性3d - 金属（I）配合物的合成与表征。在固态下，这些金属（I）配合物要么以孤立分子形式存在（钴），要么是钾离子连接的一维配位聚合物的一部分（铬 - 铁）。在溶液中，钾阳离子要么在金属硅酰胺的配体球内配位，要么根据溶剂与配合物分离。对于铁，我们展示了可以使用钠或锂金属来还原金属（II）前体。然而，在这些情况下，只有使用合适的冠醚进行阳离子分离后才能分离得到铁（I）配合物。此外，在钴和铁的情况下，中性金属（I）配合物用于引入NBu作为有机阳离子。与二苯乙炔反应时，分子内阳离子络合的影响得到进一步证明，这导致键形成过程和氧化还原歧化，而不是形成η - 炔烃配合物。
