Perturbation of the charge density between two bridged Mo₂ centers: the remote substituent effects

A series of terephthalate-bridged dimolybdenum dimers with various formamidinate ancillary ligands, denoted as [Mo2(ArNCHNAr)3]2(μ-O2CC6H4CO2) (Ar = p-XC6H4, with X = OCH3 (1), CH3 (2), F (3), Cl (4), OCF3 (5), and CF3 (6)), has been synthesized and studied in terms of substituent effects on electron delocalization between the two dimetal sites. X-ray structural analyses show that these complexes share the same molecular scaffold with the para-substituents (X) being about 8 Å away from the Mo2 center. It is found that the remote substituents have the capability to tune the electronic properties of the complexes. For the series 1 to 6, the metal-metal bond distances (d(Mo-Mo)) decrease slightly and continuously; the potential separations (ΔE(1/2)) for the two successive one-electron oxidations decrease constantly, and the metal to ligand transition energies (λ(max)) increase in order. More interestingly, the two types of methine protons, H(∥) on the horizontal and H(⊥) on the vertical ligands with respect to the plane defined by the Mo-Mo bond vectors and bridging ligand, display separate resonant signals δ(∥) and δ(⊥) in the NMR spectra. The displacements of the chemical shifts, Δδ(∥-⊥) = δ(∥) - δ(⊥), are getting smaller as the substituents vary from electron-donating to -withdrawing. These results show that the peripheral groups on the [Mo2] units function to fine-tune the metal-metal interactions crossing the bridging ligand. The experimental parameters, ΔE(1/2), λ(max), and Δδ(∥-⊥), which are linearly related with the Hammett constants (σ(X)) of the X groups, can be used to probe the charge density on the two [Mo2] units and the electronic delocalization between them.