A mononuclear hydroxomanganese(III) complex was synthesized utilizing the N5 amide-containing ligand 2-[bis(pyridin-2-ylmethyl)]amino-N-2-methyl-quinolin-8-yl-acetamidate (dpaq(2Me) ). This complex is similar to previously reported [Mn(III)(OH)(dpaq(H))](+) [Inorg. Chem. 2014, 53, 7622-7634] but contains a methyl group adjacent to the hydroxo moiety. This α-methylquinoline group in [Mn(III)(OH)(dpaq(2Me))](+) gives rise to a 0.1 Å elongation in the Mn-N(quinoline) distance relative to [Mn(III)(OH)(dpaq(H))](+). Similar bond elongation is observed in the corresponding Mn(II) complex. In MeCN, [Mn(III)(OH)(dpaq(2Me))](+) reacts rapidly with 2,2',6,6'-tetramethylpiperidine-1-ol (TEMPOH) at -35 °C by a concerted proton-electron transfer (CPET) mechanism (second-order rate constant k2 of 3.9(3) M(-1) s(-1)). Using enthalpies and entropies of activation from variable-temperature studies of TEMPOH oxidation by [Mn(III)(OH)(dpaq(2Me))](+) (ΔH(‡) = 5.7(3) kcal(-1) M(-1); ΔS(‡) = -41(1) cal M(-1) K(-1)), it was determined that [Mn(III)(OH)(dpaq(2Me))](+) oxidizes TEMPOH ∼240 times faster than [Mn(III)(OH)(dpaq(H))](+). The [Mn(III)(OH)(dpaq(2Me))](+) complex is also capable of oxidizing the stronger O-H and C-H bonds of 2,4,6-tri-tert-butylphenol and xanthene, respectively. However, for these reactions [Mn(III)(OH)(dpaq(2Me))](+) displays, at best, modest rate enhancement relative to [Mn(III)(OH)(dpaq(H))](+). A combination of density function theory (DFT) and cyclic voltammetry studies establish an increase in the Mn(III)/Mn(II) reduction potential of [Mn(III)(OH)(dpaq(2Me))](+) relative to [Mn(III)(OH)(dpaq(H))](+), which gives rise to a larger driving force for CPET for the former complex. Thus, more favorable thermodynamics for [Mn(III)(OH)(dpaq(2Me))](+) can account for the dramatic increase in rate with TEMPOH. For the more sterically encumbered substrates, DFT computations suggest that this effect is mitigated by unfavorable steric interactions between the substrate and the α-methylquinoline group of the dpaq(2Me) ligand. The DFT calculations, which reproduce the experimental activation free energies quite well, provide the first examination of the transition-state structure of mononuclear Mn(III)(OH) species during a CPET reaction.

Mononuclear MnIII–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 dpaq5R) contained a substituent R (where R = OMe, Cl, and NO2) at the 5-position of the quinolinyl group. Generation of the MnIII complexes was achieved by either O2 oxidation of MnII precursors (for [MnII(dpaq5OMe)]+ and [MnII(dpaq5Cl)]+ or PhIO oxidation (for [MnII(dpaq5NO2 )]+). For each oxidized complex, 1H NMR experiments provided evidence of a water-dependent equilibrium between paramagnetic [MnIII(OH)­(dpaq5R)]+ and an antiferromagnetically coupled [MnIIIMnIII(μ-O)­(dpaq5R)2]2+ species in acetonitrile, with the addition of water favoring the MnIII–hydroxo species. This conversion could also be monitored by electronic absorption spectroscopy. Solid-state X-ray crystal structures for each [MnIIIMnIII(μ-O)­(dpaq5R)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 [MnIII(OH)­(dpaq5Cl)]­(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 [MnIII(OH)­(dpaq5R)]+ complexes was demonstrated through shifts in a number of 1H NMR resonances, as well as a steady increase in the MnIII/II cyclic voltammetry peak potential in the order [MnIII(OH)­(dpaq5OMe)]+ < [MnIII(OH)­(dpaq)]+ < [MnIII(OH)­(dpaq5Cl)]+ < [MnIII(OH)­(dpaq5NO2 )]+. These changes in oxidizing power of the MnIII–hydroxo adducts translated to only modest rate enhancements for TEMPOH oxidation by the [MnIII(OH)­(dpaq5R)]+ complexes, with the most reactive [MnIII(OH)­(dpaq5NO2 )]+ complex showing a second-order rate constant only 9-fold larger than that of the least reactive [MnIII(OH)­(dpaq5OMe)]+ complex. These modest rate changes were understood on the basis of density functional theory (DFT)-computed pK a values for the corresponding [MnII(OH2)­(dpaq5R)]+ 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 MnIII–hydroxo unit.