Structure and Reactivity of (μ-Oxo)dimanganese(III,III) and Mononuclear Hydroxomanganese(III) Adducts Supported by Derivatives of an Amide-Containing Pentadentate Ligand

Abstract

Mononuclear Mn^III-hydroxo and dinuclear (μ-oxo)dimanganese(III,III) complexes were prepared using derivatives of the pentadentate, amide-containing dpaq ligand (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino- N-quinolin-8-yl-acetamidate). Each of these ligand derivatives (referred to as dpaq^5R) contained a substituent R (where R = OMe, Cl, and NO₂) at the 5-position of the quinolinyl group. Generation of the Mn^III complexes was achieved by either O₂ oxidation of Mn^II precursors (for [Mn^II(dpaq^5OMe)]⁺ and [Mn^II(dpaq^5Cl)]⁺ or PhIO oxidation (for [Mn^II(dpaq^5NO₂)]⁺). For each oxidized complex, ¹H NMR experiments provided evidence of a water-dependent equilibrium between paramagnetic [Mn^III(OH)(dpaq^5R)]⁺ and an antiferromagnetically coupled [Mn^IIIMn^III(μ-O)(dpaq^5R)₂]²⁺ species in acetonitrile, with the addition of water favoring the Mn^III-hydroxo species. This conversion could also be monitored by electronic absorption spectroscopy. Solid-state X-ray crystal structures for each [Mn^IIIMn^III(μ-O)(dpaq^5R)₂](OTf)₂ complex revealed a nearly linear Mn-O-Mn core (angle of ca. 177°), with short Mn-O distances near 1.79 Å, and a Mn···Mn separation of 3.58 Å. X-ray crystallographic information was also obtained for the mononuclear [Mn^III(OH)(dpaq^5Cl)](OTf) complex, which has a short Mn-O(H) distance of 1.810(2) Å. The influence of the 5-substituted quinolinyl moiety on the electronic properties of the [Mn^III(OH)(dpaq^5R)]⁺ complexes was demonstrated through shifts in a number of ¹H NMR resonances, as well as a steady increase in the Mn^III/II cyclic voltammetry peak potential in the order [Mn^III(OH)(dpaq^5OMe)]⁺ < [Mn^III(OH)(dpaq)]⁺ < [Mn^III(OH)(dpaq^5Cl)]⁺ < [Mn^III(OH)(dpaq^5NO₂)]⁺. These changes in oxidizing power of the Mn^III-hydroxo adducts translated to only modest rate enhancements for TEMPOH oxidation by the [Mn^III(OH)(dpaq^5R)]⁺ complexes, with the most reactive [Mn^III(OH)(dpaq^5NO₂)]⁺ complex showing a second-order rate constant only 9-fold larger than that of the least reactive [Mn^III(OH)(dpaq^5OMe)]⁺ complex. These modest rate changes were understood on the basis of density functional theory (DFT)-computed p K_a values for the corresponding [Mn^II(OH₂)(dpaq^5R)]⁺ complexes. Collectively, the experimental and DFT results reveal that the 5-substituted quinolinyl groups have an inverse influence on electron and proton affinity for the Mn^III-hydroxo unit.