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The metal complexes [M{HB(hpp)}2(CO)4] (M = Cr, Mo or W) and [M(cod){HB(hpp)}2Cl] (M = Rh or Ir) of the doubly-base stabilized diborane(4) ligand [HB(hpp)]2 were fully characterized and their bonding nature was investigated in detail. While bonding in the group 6 complexes predominantly occurs through the hydrogen atoms, the metal–ligand interaction in the group 9 complexes can be regarded as an early stage oxidative addition of the boron–boron bond leading to diboryl compounds.
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