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.
