Insights into the hydrolytic chemistry of molybdocene dichloride based on a theoretical mechanistic study

Molecular Modeling of Bioorganometallic Compounds: Thermodynamic Properties of Molybdocene–Glutathione Complexes and Mechanism of Peptide Hydrolysis

“…By combining the COSMO‐B3LYP free energies of the [Cp 2 Mo(H 2 O) 2 ] 2+ (aq) and [Cp 2 Mo(OH)(H 2 O)] + (aq) species with the experimental p K a value, we derived a Δ G solv (H + ) value of −253.3 kcal mol −1 , which is close to typical literature values 46. As similarly done in previous work,26 we added the term −2.303 RT pH to G (H + ) to correct the standard state of H + at pH 7.0.…”

“…In previous work, we have examined the ability of the B3LYP functional complemented with the DFT‐D3 dispersion correction for studying mononuclear [Cp 2 Mo(L)(L′)] complexes, where L, L′=H 2 O, OH − , H 2 S, SH − and Cl − 25. 26 For these complexes, the B3LYP+DFT‐D3 calculations provide reaction energies for the relevant protonation and ligand‐exchange processes in the gas phase that have a mean unsigned difference of 1.9 kcal mol −1 with respect to reference values predicted by high‐level CCSD(T) calculations.…”

A combined semiempirical and DFT computational protocol for studying bioorganometallic complexes: Application to molybdocene–cysteine complexes

“…The quality of the theoretical results can be improved by refining the electronic energies through the combination of B3LYP/aug‐cc‐pVTZ energies with the DFT‐D3 dispersion correction. According to the validation calculations summarized in Supporting Information Table S4 and Figure S1 as well as those reported in a previous work, the B3LYP + DFT‐D3 calculations provide nearly identical reaction energies for relevant protonation and ligand exchange processes in the gas phase as those predicted by the highly correlated CCSD(T)/aug‐cc‐pVTZ(‐ f )//MP2/aug‐cc‐pVTZ level of theory. For example, the reaction energy for the [Cp 2 Mo(H 2 S)] 2+ + H 2 O → [Cp 2 Mo(H 2 O)] 2+ + H 2 S process amounts to −4.4 (B3LYP‐D3) and −4.5 (CCSD(T)) kcal/mol whereas the corresponding deprotonation energies of the [Cp 2 Mo(H 2 S)] 2+ complex are 137.3 (B3LYP+DFT‐D3) and 136.6 kcal/mol (CCSD(T)) (the equivalent PM6 energies have absolute errors of tens of kcal/mol; see Supporting Information Table S4).…”

“…In a previous work, we have examined the reliability of the B3LYP functional for studying mononuclear [Cp 2 Mo(L)(L')] complexes with L, L' = H 2 O, OH − and Cl − . Herein, we further examine the ability of the B3LYP functional complemented with the DFT‐D3 dispersion correction to reproduce the gas‐phase energetics of similar model complexes with L, L' = H 2 S, SH − .…”

[Cp2Mo(OH)(OH2)]+‐Catalyzed Hydrolysis of Mono‐ and Difunctional Ethers: Theoretical Understanding of Their Divergent Reactivity

“…Experimental studies on the coordination chemistry between Cp 2 MoCl 2 and different DNA (deoxyribonucleic acid) models allowed to propose that [Cp 2 Mo(OH)(OH 2 )] + is the dominant species at physiological pH and, therefore, the active species in chemical transformations catalyzed or mediated by Cp 2 MoCl 2 in water . A theoretical study carried out in our laboratory has confirmed this fact, but it has also revealed the reactive role of the species [Cp 2 Mo(OH)] + . The presence of an open coordination site and an internal hydroxo ligand in these hydroxo complexes significantly enhances the catalytic effectiveness of aqueous molybdocenes.…”