Unveiling the molecular mechanism of Mn and Zn-catalyzed Ullmann-type C-O cross-coupling reactions

A detailed theoretical study delving into the molecular mechanisms of the Ullmann-type O-arylation reactions catalyzed by manganese and zinc metal ions has been investigated with the aid of the density functional theory (DFT) method. In contrast to the redox-active mechanisms proposed for classical Ullmann-type condensation reaction, a redox-neutral mechanism involving σ-bond metathesis emerged as the most appealing pathway for the investigated high-valent Mn(II) and Zn(II)-catalyzed O-arylation reactions. The mechanism remains invariant with respect to the nature of the central metal, ligand, base, etc. This unusuality in the mechanism has been dissected by considering three cases: ligand-free and ligand-assisted Mn(II)-catalyzed O-arylation reaction and ligand-assisted Zn(II)-catalyzed O-arylation reactions. In each class, a metal phenoxide species was identified as the active catalyst. The unusual mechanistic trends observed in these C-O cross-coupling reactions could be attributed to the stable electronic configurations (d⁵, d¹⁰) combined with the higher oxidation states of the catalytic metal centers (Mn(II), Zn(II)). The exploration into the electronic effects of functional groups in controlling the reaction feasibility within each metal variant disclosed a consistent trend irrespective of the transition metal catalyst involved in the reaction. It was found that the introduction of electron-withdrawing groups at the para-position of organic halide lowers the energy of their lowest unoccupied molecular orbitals (LUMO), thereby lowering the HOMO-LUMO gap between the coupling partners. This study thereby revealed a comprehensive understanding of the fundamental mechanisms exhibited by high-valent first-row transition metal catalysts that could foster the development of eco-friendly protocols for preparing biaryl ether moieties.