A comprehensive theoretical study on the hydrolysis of carbonyl sulfide in the neutral water.

The detailed hydration mechanism of carbonyl sulfide (COS) in the presence of up to five water molecules has been investigated at the level of HF and MP2 with the basis set of 6-311++G(d, p). The nucleophilic addition of water molecule occurs in a concerted way across the C==S bond of COS rather than across the C==O bond. This preferential reaction mechanism could be rationalized in terms of Fukui functions for the both nucleophilic and electrophilic attacks.

Distinct pi-bonding capability between phosphinidene and phosphonium ion: a computational study.

The heavy dipnictenes (RE=ER, where E=P, As, Sb, and Bi with the substituent R) have essentially planar geometry and appreciable strength in pi-bonding, unlike related heavier main group 14 analogues of alkenes as concluded recently by Power. This work demonstrated that the protonated pnictenes behave more like the heavy carbene for their weak pi-bonding character from the computational study with the B3LYP/6-311++G** method. For example, although both phosphinidene (HP) and the phosphonium ion (H2P+) are isoelectronic to silylenes, the pi-bonding tendency of the former is rather strong and it forms a planar adduct with both the stable carbene and stable silylene ((HCNH)2E, where E=C and Si).

Theoretical study on the identity ion pair SN2 reactions of LiX with CH3SX (X=Cl, Br, and I): structure, mechanism, and potential energy surface.

Three archetypal ion pair nucleophilic substitution reactions at the methylsulfenyl sulfur atom LiX+CH3SX-->XSCH3+LiX (X=Cl, Br, and I) are investigated by the modified Gaussian-2 theory. Including lithium cation in the anionic models makes the ion pair reactions proceed along an SN2 mechanism, contrary to the addition-elimination pathway occurring in the corresponding anionic nucleophilic substitution reactions X-+CH3SX-->XSCH3+X-. Two reaction pathways for the ion pair SN2 reactions at sulfur, inversion and retention, are proposed.

Computational studies on stable triplet states of heteroacetylenes and the effects of halogen substituents.

This paper describes theoretical studies of halogen-substituted heteroacetylenes (XCMY, M = Si and Ge; X, Y = H, Cl and F) performed at the QCISD(T)/6-311G//QCISD/6-31G level of theory. The electronegative halogen substituents destabilize the singlet state such that the triplet state tends to become favorable. The triplet state has the bifunctional electronic structure of a triplet carbene joined to a heavy singlet carbene.

Ene reaction of arynes with alkynes.

Arynes, generated in situ from ortho-silylaryl triflates, undergo ene reaction with alkynes possessing propargylic hydrogen in the presence of KF/18-crown-6 in THF at room temperature to give substituted phenylallenes. Various terminal and internal alkynes as well as different arynes can be used to give the corresponding phenylallenes in good to moderate yields. The reaction of alkyne without propargylic hydrogen gave an acetylenic C-H addition product (a phenylalkyne) and a dehydro Diels-Alder product (a phenanthrene).

Ab initio computational insight into the ion-pair S(N)2 reaction of lithium isothiocyanate and methyl fluoride in the gas phase and in acetone solution.

The ion-pair S(N)2 reaction LiNCS + CH3F with two mechanisms, inversion and retention, was investigated at the MP2(full)/6-311+G**//HF/6-311+G** level in the gas phase and in acetone solution. All HF-optimized structures were confirmed by vibrational frequency analysis. Based on IRC analyses, eight possible reaction pathways in the title reaction are proposed.

Modified Gaussian-2 level investigation of the identity ion-pair SN2 reactions of lithium halide and methyl halide with inversion and retention mechanisms.

Identity ion-pair S(N)2 reactions LiX + CH(3)X --> XCH(3) + LiX (X = F, Cl, Br, and I) have been investigated in the gas phase and in solution at the level of the modified Gaussian-2 theory. Two possible reaction mechanisms, inversion and retention, are discussed. The reaction barriers relative to the complexes for the inversion mechanism [DeltaH(cent) ( not equal )(inv)] are found to be much higher than the corresponding values for the gas phase anionic S(N)2 reactions, decreasing in the following order: F (263.

Cycloadditions of 16-Electron 1,3-Dipoles with Ethylene. A Density Functional and CCSD(T) Study.

The 1,3-dipolar cycloaddition (DC) reactions of ethylene with nitrile ylide (CNC), nitrile imine (CNN), nitrile oxide (CNO), diazomethane (NNC), azine (NNN), and nitrous oxide (NNO) in the gas phase were examined using the density functional theory and CCSD(T) calculations. All of the structures, including the precursor complexes and the transition structures, were completely optimized at the B3LYP/6-31G level with single-point energies evaluated at CCSD(T)/6-311G. The theoretical results suggest that the activation energies for the DC reactions of nitrile-type molecules (CNC, CNN, and CNO) are small (5.

Theoretical Study of Reactions of Arduengo-Type Carbene, Silylene, and Germylene with CH(4).

The potential energy surfaces corresponding to the reaction of cyclic, unsaturated diaminocarbene (DAC), -silylene (DAS), and -germylene (DAG) with methane have been investigated by employing the B3LYP and CCSD(T) levels of theory. Our model calculations demonstrate that the electronic perturbation effect should play a significant role in determining the magnitude of their singlet-triplet splitting. Namely, the singlet-triplet gap of DAC, DAS, and DAG shows the opposite order as the parent compounds (CH(2), SiH(2), and GeH(2)), as well as the compounds with pi-donor substituents (C(NH(2))(2), Si(NH(2))(2), and Ge(NH(2))(2)).