Reversible Pt^II–CH₃ deuteration without methane loss: metal–ligand cooperation vs. ligand-assisted Pt^II-protonation

Abstract

Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo complete deuteration of Pt–CH3 fragments in ∼5 h without loss of methane to form (dpk)PtII(CD3)2 in virtually quantitative yield.

Protonolysis of BH4– Leads to Intermediacy of BH3-σ(H2) That Evolves H2 and Furnishes Borane as the Key Reducing Agent

“…The free energies of methanol as reacting solvent and H 3 O + (at pH 9.7, cf. Scheme ) were corrected for the change in standard state. , The free energy of solvated methoxide was calculated by adding the free energy of solvation of methoxide (−104.5 kcal/mol) to the gas-phase free energy, a protocol that we have demonstrated earlier to produce reliable free energies in the context of Pt-mediated C–H­(D) reductive coupling. Ground-state and transition-state (TS) geometries corresponded to exactly zero and one imaginary frequency, respectively.…”

Cp* non-innocence and the implications of (η4-Cp*H)Rh intermediates in the hydrogenation of CO2, NAD+, amino-borane, and the Cp* framework – a computational study

“…6,9,38 Since solvation of hard bases such as OH − by implicit solvation models (e.g. SMD) can lead to significant errors, [39][40][41][42] explicit water molecules were used for solvation of both free hydroxide and the transition states for (de)protonation (see the ESI †). The connectivity of transition states to the starting materials and products was verified via intrinsic reaction coordinate (IRC) calculations.…”

“…The connectivity of transition states to the starting materials and products was verified via intrinsic reaction coordinate (IRC) calculations. Free energies of reactants were corrected for the change in the standard states [42][43][44] (see the ESI †).…”