The interplay of covalency, cooperativity, and coupling strength in governing C-H bond activation in Ni₂E₂ (E = O, S,...

Dinickel dichalcogenide complexes hold vital multifaceted significance across catalysis, electron transfer, magnetism, materials science, and energy conversion. Understanding their structure, bonding, and reactivity is crucial for all aforementioned applications. These complexes are classified as dichalcogenide, subchalcogenide, or chalcogenide based on metal oxidation and coordinated chalcogen, and due to the associated complex electronic structure, ambiguity often lingers about their classification. In this work, using DFT, CASSCF/NEVPT2, and DLPNO-CCSD(T) methods, we have studied in detail [(NiL)₂(E₂)] (L = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane; E = O, S, Se and Te) complexes and explored their reactivity towards C-H bond activation for the first time. Through a comprehensive analysis of the structure, bonding, and reactivity of a series of [(NiL)₂(E₂)] complexes with E = O, S, Se, and Te, our computational findings suggest that {Ni₂O₂} and {Ni₂S₂} are best categorised as dichalcogenide-type complexes. In contrast, {Ni₂Se₂} and {Ni₂Te₂} display tendencies consistent with the subchalcogenide classification, and this aligns with the earlier structural correlation proposed (Berry and co-workers, J. Am. Chem. Soc. 2015, 137, 4993) reports on the importance of the E-E bond strength. Our study suggests the reactivity order of {Ni₂O₂} > {Ni₂S₂} > {Ni₂Se₂} > {Ni₂Te₂} for C-H bond activation, and the origin of the difference in reactivity was attributed to the difference in the Ni-E bond covalency, and electronic cooperativity between two Ni centres that switch among the classification during the reaction. Further non-adiabatic analysis at the C-H bond activation step demonstrates a decrease in coupling strength as we progress down the group, indicating a correlation with metal-ligand covalency. Notably, the reactivity trend is found to be correlated to the strength of the antiferromagnetic exchange coupling constant J via developing a magneto-structural-barrier map - offering a hitherto unknown route to fine-tune the reactivity of this important class of compound.