Effect of Lewis Acids on the Structure and Reactivity of a Mononuclear Hydroxomanganese(III) Complex

The addition of Sc(OTf)₃ and Al(OTf)₃ to the mononuclear Mn^III-hydroxo complex [Mn^III(OH)(dpaq)]⁺ (1) gives rise to new intermediates with spectroscopic properties and chemical reactivity distinct from those of [Mn^III(OH)(dpaq)]⁺. The electronic absorption spectra of [Mn^III(OH)(dpaq)]⁺ in the presence of Sc(OTf)₃ (1-Sc^III) and Al(OTf)₃ (1-Al^III) show modest perturbations in electronic transition energies, consistent with moderate changes in the Mn^III geometry. A comparison of ¹H NMR data for 1 and 1-Sc^III confirm this conclusion, as the ¹H NMR spectrum of 1-Sc^III shows the same number of hyperfine-shifted peaks as the ¹H NMR spectrum of 1. These ¹H NMR spectra, and that of 1-Al^III, share a similar chemical-shift pattern, providing firm evidence that these Lewis acids do not cause gross distortions to the structure of 1. Mn K-edge X-ray absorption data for 1-Sc^III provide evidence of elongation of the axial Mn-OH and Mn-N(amide) bonds relative to those of 1. In contrast to these modest spectroscopic perturbations, 1-Sc^III and 1-Al^III show greatly enhanced reactivity toward hydrocarbons. While 1 is unreactive toward 9,10-dihydroanthracene (DHA), 1-Sc^III and 1-Al^III react rapidly with DHA (k₂ = 0.16(1) and 0.25(2) M^-1 s^-1 at 50 °C, respectively). The 1-Sc^III species is capable of attacking the much stronger C-H bond of ethylbenzene. The basis for these perturbations to the spectroscopic properties and reactivity of 1 in the presence of these Lewis acids was elucidated by comparing properties of 1-Sc^III and 1-Al^III with the recently reported Mn^III-aqua complex [Mn^III(OH₂)(dpaq)]²⁺ ( J. Am. Chem. Soc. 2018, 140, 12695-12699). Because 1-Sc^III and 1-Al^III show ¹H NMR spectra essentially identical to that of [Mn^III(OH₂)(dpaq)]²⁺, the primary effect of these Lewis acids on 1 is protonation of the hydroxo ligand caused by an increase in the Brønsted acidity of the solution.