The water-mediated neutral hydrolysis mechanism of carbonyl sulfide (OCS) has been re-examined using the hybrid supramolecule/continuum models with n = 2–8 explicit water cluster at the level of MP2(fc)(CPCM)/6-311++G(d,p)//MP2(fc)(CPCM) /6-31+G(d). Present calculations indicate that the potential energy surface in water solution is different from the one in the gas-phase, and only stepwise mechanism is observed in aqueous solution, i.e., monothiocarbonic acid (H2CO2S) is formed via monothiocarbonate (OCSOH–, MTC) and its counterion, protonated water cluster, (H2O)nH3O+.

Metallaaromatics have attracted considerable interest from both experimentalists and theoreticians over the past three decades. However, most studies in this field have focused on metallabenzene, in which a CH group is replaced by a transition metal fragment. In comparison with monocyclic metallabenzenes, bicyclic metallanaphthalenes are rather limited. Thus, it is urgent to explore more synthetic approaches to this less developed system. One of the difficulties in the synthesis of metallanaphthalenes could be due to its low thermodynamic stability relative to the metal indenyl complexes.

Metallaaromatics have attracted continuing interest of both theoretical and experimental chemists since the first metallabenzene was predicted by Hoffmann and isolated by Roper. In sharp contrast to metallabenzenes, metallaphosphabenzene (MPB) is much less developed and has not been synthesized so far. Thus, developing synthetic approaches is urgent. Here we present thorough density functional theory (DFT) calculations on the thermodynamics and kinetics of the rearrangement between MPBs and the corresponding η5-phosphacyclopentadiene (η5-PCp) complexes.

Density functional theory (DFT) calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dialkyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C−H bond activation, transmetalation, reductive elimination and recycling of catalyst, each of which is constituted from different steps.

CO2 capture has attracted increasing attention owing to its contribution to global warming and climate change as a greenhouse gas. As an alternative strategy to transition-metal-based chemistry and catalysis, frustrated Lewis pairs have been developed to sequester CO2 efficiently under mild conditions. However, the mechanism of CO2 sequestration with amidophosphoranes remains unclear. Herein, we present a thorough density functional theory study on a series of amidophosphoranes.

Spectator or actor? Density functional theory calculations were performed to examine the role of the base in the nickel-catalyzed cross-coupling of aryl phosphates with arylboronic acids. Potassium phosphate was found to not act as a spectator base but was involved in the transmetalation step, as shown by a lower barrier than that of a base-free process, owing to the activation of the carbonboron bond by the base. Further experimental observations support the theoretical findings.