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Carbonylmetallates [m] À , such as [MoCp(CO) 3 ] À , [Mn(CO) 5 ] À , [Co(CO) 4 ] À , have long been successfully used in the preparation of hundreds of metal-metal bonded carbonyl complexes and clusters, in particular of the heterometallic type. We focus here on situations where [m] À can be viewed as a terminal, doubly or even triply bridging metalloligand, developing metal-metal interactions with one, two or three metal centers M, respectively. With metals M from the Groups 10-12, it is not straightforward or even impossible to rationalize the structure of the resulting clusters by applying the well-known Wade-Mingos rules. A very simple but global approach is presented to rationalize structures not obeying usual electron-counting rules by considering the anionic building blocks [m] À as metalloligands behaving formally as potential 2-, 4-or 6-electron donors, similarly to what is typically encountered with for example halido ligands. Qualitative and theoretical arguments by using DFT calculations highlight similarities between seemingly unrelated metal complexes and clusters and also entail a predicting power with high synthetic potential.

The proposed study concerns the inclusion complexation of dimethoate (DMT) in the β-cyclodextrin (β-CD) molecule cage using a 1:1 stoichiometry. The interactions between DMT and -CD were evaluated using PM7 and DFT in water and gas with base 6-31G(d,p); using the CAMB3LYP functional. All approaches agree with the optimal 3D structure, which includes full DMT inclusion in the CD cavity. Complexation, LUMO, and HOMO energies were computed. The natural bond orbital (NBO) and UV- visible calculations were determined and discussed. Additionally, the non-covalent intermolecular interactions between dimethoate and β-cyclodextrin are investigated through: reduced density gradient (RDG), non-covalent interaction (NCI) and independent gradient model (IGM) that the main forces stabilizing the examined inclusion complex are H-bond and Van Der Waals interactions. Furthermore, the energy decomposition analysis (EDA) emphasizes the importance of the H-bond as attractive interactions.

The proposed study concerns the inclusion complexation of dimethoate (DMT) in the β-cyclodextrin (β-CD) molecule cage using a 1:1 stoichiometry. The interactions between DMT and -CD were evaluated using PM7 and DFT in water and gas with base 6-31G(d,p); using the CAMB3LYP functional.All approaches agree with the optimal 3D structure, which includes full DMT inclusion in the CD cavity. Complexation, LUMO, and HOMO energies were computed. The natural bond orbital (NBO) and UV-visible calculations were determined and discussed. Additionally, the non-covalent intermolecular interactions between dimethoate and β-cyclodextrin are investigated through: reduced density gradient (RDG), non-covalent interaction (NCI) and independent gradient model (IGM) that the main forces stabilizing the examined inclusion complex are H-bond and Van Der Waals interactions. Furthermore, the energy decomposition analysis (EDA) emphasizes the importance of the H-bond as attractive interactions.

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