Experimental and Computational Insight into the Mechanism of NO Binding to Ferric Microperoxidase. The Likely Role of Tautomerization to Account for the pH Dependence.

According to the current paradigm, the metal-hydroxo bond in a six-coordinate porphyrin complex is believed to be significantly less reactive in ligand substitution than the analogous metal-aqua bond, due to a much higher strength of the former bond. Here, we report kinetic studies for nitric oxide (NO) binding to a heme-protein model, acetylated microperoxidase-11 (AcMP-11), that challenge this paradigm. In the studied pH range 7.4-12.6, ferric AcMP-11 exists in three acid-base forms, assigned in the literature as [(AcMP-11)FeIII(H2O)(HisH)] (1), [(AcMP-11)FeIII(OH)(HisH)] (2), and [(AcMP-11)FeIII(OH)(His-)] (3). From the pH dependence of the second-order rate constant for NO binding (kon), we determined individual rate constants characterizing forms 1-3, revealing only a ca. 10-fold decrease in the NO binding rate on going from 1 (kon(1) = 3.8 × 106 M-1 s-1) to 2 (kon(2) = 4.0 × 105 M-1 s-1) and the inertness of 3. These findings lead to the abandonment of the dissociatively activated mechanism, in which the reaction rate can be directly correlated with the Fe-OH bond energy, as the mechanistic explanation for the process with regard to 2. The reactivity of 2 is accounted for through the existence of a tautomeric equilibrium between the major [(AcMP-11)FeIII(OH)(HisH)] (2a) and minor [(AcMP-11)FeIII(H2O)(His-)] (2b) species, of which the second one is assigned as the NO binding target due to its labile Fe-OH2 bond. The proposed mechanism is further substantiated by quantum-chemical calculations, which confirmed both the significant labilization of the Fe-OH2 bond in the [(AcMP-11)FeIII(H2O)(His-)] tautomer and the feasibility of the tautomer formation, especially after introducing empirical corrections to the computed relative acidities of the H2O and HisH ligands based on the experimental pKa values. It is shown that the "effective lability" of the axial ligand (OH-/H2O) in 2 may be comparable to the lability of the H2O ligand in 1.

Spin-state energetics of metallocenes: How do best wave function and density functional theory results compare with the experimental data?

We benchmark the accuracy of quantum-chemical methods, including wave function theory methods [coupled cluster theory at the CCSD(T) level, multiconfigurational perturbation-theory (CASPT2, NEVPT2) and internally contracted multireference configuration interaction (MRCI)] and 30 density functional theory (DFT) approximations, in reproducing the spin-state splittings of metallocenes. The reference values of the electronic energy differences are derived from the experimental spin-crossover enthalpy for manganocene and the spectral data of singlet-triplet transitions for ruthenocene, ferrocene, and cobaltocenium. For ferrocene and cobaltocenium we revise the previous experimental interpretations regarding the lowest triplet energy; our argument is based on the comparison with the lowest singlet excitation energy and herein reported, carefully determined absorption spectrum of ferrocene. When deriving vertical energies from the experimental band maxima, we go beyond the routine vertical energy approximation by introducing vibronic corrections based on simulated vibrational envelopes. The benchmarking result confirms the high accuracy of the CCSD(T) method (in particular, for UCCSD(T) based on Hartree-Fock orbitals we find for our dataset: maximum error 0.12 eV, weighted mean absolute error 0.07 eV, weighted mean signed error 0.01 eV). The high accuracy of the single-reference method is corroborated by the analysis of a multiconfigurational character of the complete active space wave function for the triplet state of ferrocene. On the DFT side, our results confirm the non-universality problem with approximate functionals. The present study is an important step toward establishing an extensive and representative benchmark set of experiment-derived spin-state energetics for transition metal complexes.

Approaching the Complete Basis Set Limit for Spin-State Energetics of Mononuclear First-Row Transition Metal Complexes.

Convergence to the complete basis set (CBS) limit is analyzed for the problem of spin-state energetics in mononuclear first-row transition metal (TM) complexes by taking under scrutiny a benchmark set of 18 energy differences between spin states for 13 chemically diverse TM complexes. The performance of conventional CCSD(T) and explicitly correlated CCSD(T)-F12a/b calculations in approaching the CCSD(T)/CBS limits is systematically studied. An economic computational protocol is developed based on the CCSD-F12a approximation and (here proposed) modified scaling of the perturbative triples term (T#). This computational protocol recovers the relative spin-state energetics of the benchmark set in excellent agreement with the reference CCSD(T)/CBS limits (mean absolute deviation of 0.4, mean signed deviation of 0.2, and maximum deviation of 0.8 kcal/mol) and enables performing canonical CCSD(T) calculations for mononuclear TM complexes sized up to ca. 50 atoms, which is illustrated by application to heme-related metalloporphyrins. Furthermore, a good transferability of the basis set incompleteness error (BSIE) is demonstrated for spin-state energetics computed using CCSD(T) and other wave function methods (MP2, CASPT2, CASPT2/CC, NEVPT2, and MRCI + Q), which justifies efficient focal-point approximations and simplifies the construction of multimethod benchmark studies.

Spin States and Other Ligand-Field States of Aqua Complexes Revisited with Multireference ab Initio Calculations Including Solvation Effects.

High-level multireference (CASPT2, NEVPT2) calculations are reported for transition metal aqua complexes with electronic configurations from (3d)1 to (3d)8. We focus on the experimentally evidenced excitation energies to their various ligand-field states, including different spin states. By employing models accounting for both explicit and implicit solvation, we find that solvation effect may contribute up to 0.5 eV to the excitation energies depending on the charge of ion and character of the electronic transition. We further demonstrate that with an adequate choice of the active space and the energetics extrapolated to the complete basis set limit, the presently computed excitation energies are in a good agreement with the experimental data. This allows us to conclusively resolve significant discrepancies reported in earlier theory works [e.g., J. Phys. Chem. C 2014 , 118 , 29196 - 29208 ]. For the benchmark set of 19 spin-forbidden and 24 spin-allowed transitions (for which experimental data are unambiguous), we find the mean absolute error of 0.15 or 0.13 eV and the maximum error of 0.56 or 0.42 eV for CASPT2 or NEVPT2 calculations, respectively. For the particularly challenging sextet-quartet gap for [Fe(H2O)6]3+, we support our interpretation by additional calculations with multireference configuration interaction (MRCI) and coupled cluster theory up to the CCSDT(Q) level. By underlining a rather subtle interplay between the solvation and correlation effects, the findings of this Article are relevant not only for modeling and interpretation of optical spectra of transition metal complexes but also in further benchmarking of theoretical methods for the challenging problem of spin-state energetics.