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We describe a new electrochemical cycle that enables capture and release of carbon dioxide. The capture agent is benzylthiolate (RS–), generated electrochemically by reduction of benzyldisulfide (RSSR). Reaction of RS– with CO2 produces a terminal, sulfur-bound monothiocarbonate, RSCO2–, which acts as the CO2 carrier species, much the same as a carbamate serves as the CO2 carrier for amine-based capture strategies. Oxidation of the thiocarbonate releases CO2 and regenerates RSSR. The newly reported S-benzylthiocarbonate (IUPAC name benzylsulfanylformate) is characterized by 1H and 13C NMR, FTIR, and electrochemical analysis. The capture–release cycle is studied in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP TFSI) and dimethylformamide. Quantum chemical calculations give a binding energy of CO2 to benzyl thiolate of −66.3 kJ mol–1, consistent with the experimental observation of formation of a stable CO2 adduct. The data described here represent the first report of...

Here we report the electrocatalytic reduction of protons to hydrogen by a novel S2P2 coordinated nickel complex, [Ni(bdt)(dppf)] (bdt = 1,2-benzenedithiolate, dppf = 1,1'-bis(diphenylphosphino)ferrocene). The catalysis is fast and efficient with a turnover frequency of 1240 s(-1) and an overpotential of only 265 mV for half activity at low acid concentrations. Furthermore, catalysis is possible using a weak acid, and the complex is stable for at least 4 h in acidic solution. Calculations of the system carried out at the density functional level of theory (DFT) are consistent with a mechanism for catalysis in which both protonations take place at the nickel center.

The nature and origin of the pi-H interaction in both the ethene (olefinic) and benzene (aromatic) complexes of the first-row hydrides (BH(3), CH(4), NH(3), H(2)O, and HF) has been investigated by carrying out high level ab initio calculations. The results indicate that the strength of the pi-H interaction is enhanced as one progresses from CH(4) to HF. Unlike conventional H-bonds, this enhancement cannot be simply explained by the increase in electrostatic interactions or the electronegativity of the atom bound to the pi H-bonded proton. The contributions of each of the attractive (electrostatic, inductive, dispersive) and repulsive exchange components of the total binding energy are important. Thus, the inductive energy is highly correlated to the olefinic pi-H interaction as we progress from CH(3) to HF. On the other hand, both electrostatic and inductive energies are important in the description of the aromatic pi-H interaction. In either case, the contribution of dispersion energies is vital to obtain an accurate estimate of the binding energy. We also elaborate on the correlation of various interaction energy components with changes in geometries and vibrational frequencies. The red-shift of the nu(Y-H) mode is highly correlated to the inductive interaction. The dramatic increase in the exchange repulsion energies of these pi complexes as we progress from CH(4) to HF can be correlated to the blue-shift of the highly IR active out-of-plane bending mode of the pi system.

Among the several weak intermolecular interactions pervading chemistry and biology, the NH-pi interaction is one of the most widely known. Nevertheless its weak nature makes it one of the most poorly understood and characterized interactions. The present study details the results obtained on gas-phase complexes of ammonia with various substituted pi systems using both laser vibrational spectroscopy and ab initio calculations. The spectroscopic measurements carried out by applying one-color resonant two-photon ionization (R2PI) and IR-vibrational predissociation spectroscopy in the region of the NH stretches yield the first experimental NH stretching shifts of ammonia upon its interaction with various kinds of pi-systems. The experiments were complemented by ab initio calculations and energy decompositions, carried out at the second-order Møller-Plesset (MP2) level of theory. The observed complexes show characteristic vibrational spectra which are very similar to the calculated ones, thereby allowing an in-depth analysis of the interaction forces and energies. The interaction energy of the conformers responsible for the observed vibrational spectra has the maximum contribution from dispersion energies. This implies that polarizabilities of the pi-electron systems play a very important role in governing the nature and geometry of the NH-pi interaction. The larger polarizability of ammonia as compared to water and the tendency to maximize the dispersion energy implies that the characteristics of the NH-pi interactions are markedly different from that of the corresponding OH-pi interactions.

The edge-to-face interactions for either axially or facially substituted benzenes are investigated by using ab initio calculations. The predicted maximum energy difference between substituted and unsubstituted systems is approximately 0.7 kcal/mol (approximately 1.2 kcal/mol if substituents are on both axially and facially substituted positions). In the case of axially substituted aromatic systems, the electron density at the para position is an important stabilizing factor, and thus the stabilization/destabilization by substitution is highly correlated to the electrostatic energy. This results in its subsequent correlation with the polarization and charge transfer. Thus, the stabilization/destabilization by substitution is represented by the sum of electrostatic energy and induction energy. On the other hand, the facially substituted aromatic system depends on not only the electron-donating ability responsible for the electrostatic energy but also the dispersion interaction and exchange repulsion. Although the dispersion energy is the most dominating interaction in both axial and facial substitutions, it is almost canceled by the exchange repulsion in the axial substitution, whereas in the facial substitution, together with the exchange repulsion it augments the electrostatic energy. The systems with electron-accepting substituents (NO2, CN, Br, Cl, F) favor the axial substituent conformation, while those with electron-donating substituents (NH2, CH3, OH) favor the facial substituent conformation. The interactions for the T-shape complex systems of an aromatic ring with other counterpart such as H2, H2O, HCl, and HF are also studied.