Dative and electron-sharing bonding in transition metal compounds.

Quantum chemical calculations using density functional theory at the BP86-D3(BJ)/def2-TZVPP level of theory are reported for transition metal compounds [TM]-L in high and low oxidation states involving carbene, carbyne, alkene, and alkyne ligands L. The nature of the [TM]-L bond is analyzed with the energy decomposition analysis - natural orbitals for chemical valence (EDA-NOCV) method. The calculations reveal that transition metal compounds with ligands, that are typically classified as donor-acceptor complexes possessing dative bonds (Fischer-type carbenes and carbynes, alkene, and alkyne complexes) or as TM compounds with electron-sharing bonds (Schrock-type carbenes and carbynes, metallacyclopropanes, and metallacyclopropenes), exhibit significant differences between the orbital interactions when closed-shell or open shell fragments are used. Fischer-type carbene complexes have much lower orbital interaction (ΔEorb ) values when singlet fragments are employed compared to triplet fragments. In contrast, singlet and triplet fragments of Schrock-type carbene complexes give similar ΔEorb values. The best description for Fischer-type carbyne complexes is found for neutral fragments in their electronic doublet state, which engage in a mixture of dative bonding (σ donation and π backdonation) and one electron-sharing π bond. The EDA-NOCV calculations of Schrock-type carbynes using open-shell species in their quartet electronic state give similar ΔEorb values as neutral fragments in their electronic doublet state. Alkene and alkyne complexes, but also metallacyclic species, are best described with singlet fragments, but the difference between the ΔEorb values for dative bonding and electron-sharing bonding using triplet fragments becomes much smaller for molecules that are considered as metallacycles. © 2018 Wiley Periodicals, Inc.