HAA by the first {Mn(iii)OH} complex with all O-donor ligands.

There is considerable interest in MnOHx moieties, particularly in the stepwise changes in those O-H bonds in tandem with Mn oxidation state changes. The reactivity of aquo-derived ligands, {MOHx}, is also heavily influenced by the electronic character of the other ligands. Despite the prevalence of oxygen coordination in biological systems, preparation of mononuclear Mn complexes of this type with all O-donors is rare. Herein, we report several Mn complexes with perfluoropinacolate (pinF)2- including the first example of a crystallographically characterized mononuclear {Mn(iii)OH} with all O-donors, K2[Mn(OH)(pinF)2], 3. Complex 3 is prepared via deprotonation of K[Mn(OH2)(pinF)2], 1, the pKa of which is estimated to be 18.3 ± 0.3. Cyclic voltammetry reveals quasi-reversible redox behavior for both 1 and 3 with an unusually large ΔEp, assigned to the Mn(iii/ii) couple. Using the Bordwell method, the bond dissociation free energy (BDFE) of the O-H bond in {Mn(ii)-OH2} is estimated to be 67-70 kcal mol-1. Complex 3 abstracts H-atoms from 1,2-diphenylhydrazine, 2,4,6-TTBP, and TEMPOH, the latter of which supports a PCET mechanism. Under basic conditions in air, the synthesis of 1 results in K2[Mn(OAc)(pinF)2], 2, proposed to result from the oxidation of Et2O to EtOAc by a reactive Mn species, followed by ester hydrolysis. Complex 3 alone does not react with Et2O, but addition of O2 at low temperature effects the formation of a new chromophore proposed to be a Mn(iv) species. The related complexes K(18C6)[Mn(iii)(pinF)2], 4, and (Me4N)2[Mn(ii)(pinF)2], 5, have also been prepared and their properties discussed in relation to complexes 1-3.