Understanding, Modulating, and Leveraging Transannular M → Z Interactions

Density functional theory calculations have been performed on metallatranes featuring a group 13 elements at the bridgehead position to understand the factors that influence the nature of the M center dot center dot center dot Z (M = Fe, Co, Ni; Z = Al, Ga, In) interaction present in these complexes and the resultant reactivity at the metal center. The strength of the M center dot center dot center dot Z interaction increases with the increase in the size and polarizability of the bridgehead group 13 elements. The calculated reaction free energies (Delta G degrees values) for binding of different Lewis bases to the metallatranes are found to be significantly more exergonic for the larger In(III) ions. Quantum theory of atoms in molecules calculations reveal the covalent nature of the M center dot center dot center dot Z interactions, while the EDA-NOCV analysis indicates the strong binding ability of these metallatranes not only to different sigma-donor and pi-acceptor ligands but also to relatively inert species, such as N-2.

Automated summary

Density functional theory calculations were conducted on metallatranes containing group 13 elements at the bridgehead position to study the M center dot center dot center dot Z interaction and reactivity at the metal center. The strength of the M center dot center dot center dot Z interaction was found to increase with the size and polarizability of the bridgehead group 13 elements. The binding of Lewis bases to the metallatranes was significantly more exergonic for the larger In(III) ions.