10.1021/ja205037t
The research focuses on the synthesis, characterization, and electrochemical analysis of a new family of electron-deficient tris(aryl)boranes, B(C6F5)3n(C6Cl5)n (n = 13), which allows for an investigation into the steric and electronic effects resulting from the gradual replacement of C6F5 with C6Cl5 ligands. The experiments involved the use of various reactants such as C6Cl5Li, BCl3, CuC6F5, and Zn(C6Cl5)2, among others, to synthesize the target compounds through a series of metathesis reactions and halide metathesis reactions. The synthesized compounds were structurally characterized using single crystal X-ray diffraction, and their spectroscopic properties were analyzed using 11B, 19F, and 13C NMR. Additionally, density functional theory (DFT) calculations were performed to optimize the structures and compute 11B shielding constants. The electrochemical behavior of the compounds was investigated using cyclic voltammetry, and the stability of the radical anions was assessed through EPR spectroscopy. The analyses provided insights into the electron deficiency at the boron center, the structural changes upon ligand substitution, and the correlation between electronic effects and Lewis acidity.