A systematic quantum chemical study of the bonding in d6 -transition-metal complexes, containing phosphine-stabilized, main-group-element fragments, (R3 P)2 E, as ligands (E=AlH, BH, CH+ , C), is reported. By using energy decomposition analysis, it is demonstrated that a strong M-E bond is accompanied by weak P-E bonds, and vice versa. Although the Al-M bond is, for example, found to be very strong, the weak Al-P bond suggests that the corresponding metal complexes will not be stable towards phosphine dissociation. The interaction energies for the boron(I)-based ligand are lower, but still higher than those for two-carbon-based ligands. For neutral ligands, electrostatic interactions are the dominating contributions to metal-ligand bonding, whereas for the cationic ligand a significant destabilization, with weak orbital and even weaker electrostatic metal-ligand interactions, is observed. Finally, for iron(II) complexes, it is demonstrated that different reactivity patterns are expected for the four donor groups: the experimentally observed reversible E-H reductive elimination of the borylene-based ligand (E=BH) exhibits significantly higher barriers for the protonated carbodiphosphorane (CDP) ligand (E=CH) and would proceed through different intermediates and transition states. For aluminum, such reaction pathways are not feasible (E=AlH). Moreover, it is demonstrated that the metal hydrido complexes with CDP ligands might not be stable towards reduction and isomerization to a protonated CDP ligand and a reduced metal center.
Keywords: bond theory; computational chemistry; ligand effects; main group elements; transition metals.
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