Garçon Martí, Phanopoulos Andreas, Sackman George A, Richardson Christopher, White Andrew J P, Cooper Richard I, Edwards Alison J, Crimmin Mark R
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, 82 Wood Lane, Shepherds Bush, London, W12 0BZ, UK.
Chemical Crystallography, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Angew Chem Int Ed Engl. 2022 Nov 2;61(44):e202211948. doi: 10.1002/anie.202211948. Epub 2022 Oct 5.
New heterometallic hydride complexes that involve the addition of {Mg-H} and {Zn-H} bonds to group 10 transition metals (Pd, Pt) are reported. The side-on coordination of a single {Mg-H} to Pd forms a well-defined σ-complex. In contrast, addition of three {Mg-H} or {Zn-H} bonds to Pd or Pt results in the formation of planar complexes with subtly different geometries. We compare their structures through experiment (X-ray diffraction, neutron diffraction, multinuclear NMR), computational methods (DFT, QTAIM, NCIPlot), and theoretical analysis (MO diagram, Walsh diagram). These species can be described as snapshots along a continuum of bonding between ideal trigonal planar and hexagonal planar geometries.
报道了涉及将{Mg-H}和{Zn-H}键加成到第10族过渡金属(Pd、Pt)上的新型异金属氢化物配合物。单个{Mg-H}与Pd的侧面配位形成了明确的σ配合物。相比之下,向Pd或Pt添加三个{Mg-H}或{Zn-H}键会导致形成具有细微不同几何形状的平面配合物。我们通过实验(X射线衍射、中子衍射、多核NMR)、计算方法(DFT、QTAIM、NCIPlot)和理论分析(MO图、沃尔什图)比较了它们的结构。这些物种可以描述为沿着理想三角平面和六角平面几何形状之间连续键合的快照。