Dative quadruple bonds between d10 transition metals and beryllium in BeM(PMe3)2 and BeM(CO)2 (M = Ni, Pd, and Pt) complexes: Transition metal fragments as six‐electron donor and two‐electron acceptor

The structure, chemical bonding, and reactivity of neutral 16 valence electrons (VE) transition metal complexes of beryllium, BeM(PMe3 )2 (1M-Be) and BeM(CO)2 (2M-Be, M = Ni, Pd, and Pt) were studied. The molecular orbital and EDA-NOCV analysis suggest dative quadruple bonds between the transition metal and beryllium, viz., one Be→M σ bond, one Be←M σ bond, and two Be←M π bonds. The strength of these bonding interactions varies based on the ligands coordinated to the transition metal. The Be←M σ bond is stronger than the Be→M σ bond when the ligand is PMe3, whereas the reverse order is observed when the ligand is CO. This is attributed to the higher π acceptor strength of CO as compared to PMe3 . Since these complexes have M-Be dative quadruple bonds, the beryllium center is susceptible to ambiphilic reactivity, as indicated by high proton and hydride affinity values.