Influence of Thiolate versus Alkoxide Ligands on the Stability of Crystallographically Characterized Mn(III)-Alkylperoxo Complexes.

The work described herein demonstrates the exquisite control that the inner coordination sphere of metalloenzymes and transition-metal complexes can have on reactivity. We report one of few crystallographically characterized Mn-peroxo complexes and show that the tight correlations between metrical and spectroscopic parameters, established previously by our group for thiolate-ligated RS-Mn(III)-OOR complexes, can be extended to include an alkoxide-ligated RO-Mn(III)-OOR complex. We show that the alkoxide-ligated RO-Mn(III)-OOR complex is an order of magnitude more stable (t1/2298 K = 6730 s, kobs298 K = 1.03 × 10-4 s-1) than its thiolate-ligated RS-Mn(III)-OOR derivative (t1/2293 K = 249 s, k1293 K = 2.78 × 10-3 s-1). Electronic structure calculations provide insight regarding these differences in stability. The highest occupied orbital of the thiolate-ligated derivative possesses significant sulfur character and π-backdonation from the thiolate competes with π-backdonation from the peroxo π*(O-O). DFT-calculated Mulliken charges show that the Mn ion Lewis acidity of alkoxide-ligated RO-Mn(III)-OOR (+0.451) is greater than that of thiolate-ligated RS-Mn(III)-OOR (+0.306), thereby facilitating π-backdonation from the antibonding peroxo π*(O-O) orbital and increasing its stability. This helps to explain why the photosynthetic oxygen-evolving Mn complex, which catalyzes O-O bond formation as opposed to cleavage, incorporates O- and/or N-ligands as opposed to cysS-ligands.

How Do Ring Size and π-Donating Thiolate Ligands Affect Redox-Active, α-Imino-N-heterocycle Ligand Activation?

Considerable effort has been devoted to the development of first-row transition-metal catalysts containing redox-active imino-pyridine ligands that are capable of storing multiple reducing equivalents. This property allows abundant and inexpensive first-row transition metals, which favor sequential one-electron redox processes, to function as competent catalysts in the concerted two-electron reduction of substrates. Herein we report the syntheses and characterization of a series of iron complexes that contain both π-donating thiolate and π-accepting (α-imino)-N-heterocycle redox-active ligands, with progressively larger N-heterocycle rings (imidazole, pyridine, and quinoline). A cooperative interaction between these complementary redox-active ligands is shown to dictate the properties of these complexes. Unusually intense charge-transfer (CT) bands, and intraligand metrical parameters, reminiscent of a reduced (α-imino)-N-heterocycle ligand (L•-), initially suggested that the electron-donating thiolate had reduced the N-heterocycle. Sulfur K-edge X-ray absorption spectroscopic (XAS) data, however, provides evidence for direct communication, via backbonding, between the thiolate sulfur and the formally orthogonal (α-imino)-N-heterocycle ligand π*-orbitals. DFT calculations provide evidence for extensive delocalization of bonds over the sulfur, iron, and (α-imino)-N-heterocycle, and TD-DFT shows that the intense optical CT bands involve transitions between a mixed Fe/S donor, and (α-imino)-N-heterocycle π*-acceptor orbital. The energies and intensities of the optical and S K-edge pre-edge XAS transitions are shown to correlate with N-heterocycle ring size, as do the redox potentials. When the thiolate is replaced with a thioether, or when the low-spin S = 0 Fe(II) is replaced with a high-spin S = 3/2 Co(II), the N-heterocycle ligand metrical parameters and electronic structure do not change relative to the neutral L0 ligand. With respect to the development of future catalysts containing redox-active ligands, the energy cost of storing reducing equivalents is shown to be lowest when a quinoline, as opposed to imidazole or pyridine, is incorporated into the ligand backbone of the corresponding Fe complex.

Water-soluble Fe(II)-H2O complex with a weak O-H bond transfers a hydrogen atom via an observable monomeric Fe(III)-OH.

Understanding the metal ion properties that favor O-H bond formation versus cleavage should facilitate the development of catalysts tailored to promote a specific reaction, e.g., C-H activation or H2O oxidation. The first step in H2O oxidation involves the endothermic cleavage of a strong O-H bond (BDFE = 122.7 kcal/mol), promoted by binding the H2O to a metal ion, and by coupling electron transfer to proton transfer (PCET). This study focuses on details regarding how a metal ion's electronic structure and ligand environment can tune the energetics of M(HO-H) bond cleavage. The synthesis and characterization of an Fe(II)-H2O complex, 1, that undergoes PCET in H2O to afford a rare example of a monomeric Fe(III)-OH, 7, is described. High-spin 7 is also reproducibly generated via the addition of H2O to {[Fe(III)(O(Me2)N4(tren))]2-(µ-O)}(2+) (8). The O-H bond BDFE of Fe(II)-H2O (1) (68.6 kcal/mol) is calculated using linear fits to its Pourbaix diagram and shown to be 54.1 kcal/mol less than that of H2O and 10.9 kcal/mol less than that of [Fe(II)(H2O)6](2+). The O-H bond of 1 is noticeably weaker than the majority of reported M(n+)(HxO-H) (M = Mn, Fe; n+ = 2+, 3+; x = 0, 1) complexes. Consistent with their relative BDFEs, Fe(II)-H2O (1) is found to donate a H atom to TEMPO(•), whereas the majority of previously reported M(n+)-O(H) complexes, including [Mn(III)(S(Me2)N4(tren))(OH)](+) (2), have been shown to abstract H atoms from TEMPOH. Factors responsible for the weaker O-H bond of 1, such as differences in the electron-donating properties of the ligand, metal ion Lewis acidity, and electronic structure, are discussed.