Trisulfides over disulfides: highly selective synthetic strategies, anti-proliferative activities and sustained H2S release profiles.

Temperature- and solvent-induced selective synthesis of trisulfides and disulfides is demonstrated. A remarkable selectivity was achieved using Na2S as a sulfur-transfer agent under mild, greener, catalyst-free and additive-free conditions. This study reveals trisulfides as a better model than disulfides in general for a sustained release of H2S and potent anti-cancer activities.

Geometry-Driven Iminosemiquinone Radical to Cu(II) Electron Transfer and Stabilization of an Elusive Five-Coordinate Cu(I) Complex: Synthesis, Characterization, and Reactivity with KO2.

The noninnocent ligand H2LAP(Ph) contained a bulky phenyl substituent at the ortho position to the aniline moiety. The ligand reacted with 0.5 equiv of CuCl2·2H2O in the presence of Et3N under air and provided the corresponding Cu(II)-bis(imonosemiquinone) complex (1). The complex upon oxidation by a stoichiometric amount of ferrocenium hexafluorophosphate (FcPF6) yielded the four-coordinate [Cu(II)-(imonosemiquinone)(iminoquinone)]PF6 complex (3), while the oxidation by an equivalent amount of CuCl2·2H2O produced the five-coordinate Cu(I)-bis(iminoquinone)Cl complex (2). Thus, a ligand-based oxidation followed by ligand-to-metal electron-transfer was realized for the latter oxidation process. Removal of the Cl- ion from complex 2 rendered the four-coordinate complex 4. The oxidation state of both Cu(I) and iminoquinone moieties remained unaltered upon the change in the coordination number. All the complexes were characterized by X-ray crystallography. Complexes 2, 3, and 4 were diamagnetic with an St = 0 ground state as evident by electron paramagnetic resonance (EPR) and 1H NMR measurements. The UV-vis-NIR spectra of all the complexes were dominated by charge-transfer transitions. Two oxidations and two reductions waves were noticed in the cyclic voltammogram (CV) of complex 1. Complex 2 and complex 3 underwent one oxidation and three reductions. Unlike complex 3, which experienced ligand-based oxidation, in complex 2 the oxidation was metal-centered [oxidation of Cu(I)-to-Cu(II)]. UV-vis-NIR spectral changes during the fixed-potential coulometric one-electron oxidation and thereafter EPR analysis consolidated the metal-based oxidation in complex 2. Complex 2 was air stable; however, it oxidized KO2 to oxygen molecule, and complex 1 was formed in due course as evident by UV-vis-NIR spectral changes and EPR measurements. Time dependent density functional theory calculations have been incorporated to assign the transitions that appeared in the UV-vis-NIR spectra of the complexes.

Bonding and spectroscopic analyses of N2O-CS2 and N2O-OCS heterodimer complexes and their atmospheric consequences.

Different isomers of the valence isoelectronic pairs of the heterodimers N2O-SCS and N2O-OCS were investigated using MP2 and CCSD(T) methods with the aug-cc-pVXZ (X = D, T) basis set with anharmonic frequency calculations. Interaction energies of both the heterodimers were estimated at the CBS limit and for CCSD(T)/aug-cc-pVTZ. One isomer was located for the N2O-SCS heterodimer. In the case of the N2O-OCS heterodimer, three planar slipped-parallel isomers were characterized. There was no significant change in electron density at the bond critical points (BCPs) of various intra-bonds but the presence of inter-bonds with a weak electron density at the BCPs in the complexes was found as per the results from the quantum theory of atoms in molecules (QTAIM) analysis. The interorbital interactions of the monomer in the heterodimers are discussed herein in terms of the natural bond orbital (NBO) charge transfer. Symmetry-adapted perturbation analysis was performed for all the isomers. In the case of the stable complex of N2O-SCS, induction dominated over the dispersion energy. Among the N2O-OCS isomers, the dispersion effect predominates for the most stable isomer, while for the other two isomers, the induction effect is dominant. Frequency calculations for these complexes showed a number of interactions induced by the low frequency modes in the far IR region. The atmospheric implications are also discussed for these complexes.

A theoretical investigation of the energetics and spectroscopic properties of the gas-phase linear proton-bound cation-molecule complexes, XCH(+)-N2 (X = O, S).

The structural features, spectroscopic properties, and interaction energies of the linear proton-bound complexes of OCH(+) and its sulfur analog SCH(+) with N2 were investigated using the high-level ab initio methods MP2 and CCSD(T) as well as density functional theory with the aug-cc-pVXZ (X = D, T) basis sets. The rotational constants along with the vibrational frequencies of the cation-molecule complexes are reported here. A comparison of the interaction energies of the OCH(+)-N2 and SCH(+)-N2 complexes with those of the OCH(+)-CO and OCH(+)-OC complexes was also performed. The energies of all the complexes were determined at the complete basis set (CBS) limit. CS shows higher proton affinity at the C site than CO does, so the complex OCH(+)-N2 is relatively strongly bound and has a higher interaction energy than the SCH(+)-N2 complex. Symmetry-adapted perturbation theory (SAPT) was used to decompose the total interaction energies of the complexes into the attractive electrostatic interaction energy (E elst), induction energy (E ind), dispersion energy (E disp), and repulsive exchange energy (E exch). We found that the ratio of E ind to E disp is large for these linear proton-bound complexes, meaning that inductive effects are favored in these complexes. The bonding characteristics of the linear complexes were elucidated using natural bond orbital (NBO) theory. NBO analysis showed that the attractive interaction is caused by NBO charge transfer from the lone pair on N to the σ*(C-H) antibonding orbital in XCH(+)-N2 (X = O, S). The quantum theory of atoms in molecules (QTAIM) was used to analyze the strengths of the various bonds within and between the cation and molecule in each of these proton-bound complexes in terms of the electron density at bond critical points (BCP). Graphical Abstract Linear proton-bound complexes of OCH(+)-N2 and SCH(+)-N2. In these complexes, inductive effect is favored over dispersive effect. The attractive interaction is the NBO charge transfer from N-lone pair of N2 to CH σ* antibonding orbital of XCH(+) (X = O, S).

Bonding and spectroscopic properties of complexes of SO2-O2 and SO2-N2 and its atmospheric consequences.

van der Waals complexes of sulfur dioxide (SO2) with oxygen (O2) and nitrogen (N2) have been investigated by using MP2 and aug-cc-pVXZ (X = D, T) basis set. Two minimum structures with symmetry C1 and Cs have been located at the intermolecular potential energy surface (IPES) of the complex of SO2-O2. Stacked Cs structure of SO2-O2 is found to have greater stability than C1 structure. In the case of SO2-N2, one minimum structure with Cs symmetry has been characterized. In this study, CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ and interaction energy calculation at complete basis set (CBS) limit has been employed for better energetic description. The natural bond orbital (NBO) calculation demonstrates the bonding in terms of charge transfer from X-atom lone pair of X2 (X = O or N) to the antibonding SO orbital of SO2. The strength of various intra and inter bonds in the complexes were calculated in terms of electron density at bond critical points (BCP) using quantum theory of atoms in molecules (QTAIM). Frequency calculations for these complexes show a number of interactions induced by low frequency modes in the far IR region. Symmetry adapted calculation were also computed for the complexes and is established that the ratio of dispersion to induction effect is large for the most stable conformers. The atmospheric implications are also discussed for these complexes.

Reaction of chlorine radical with tetrahydrofuran: a theoretical investigation on mechanism and reactivity in gas phase.

Reaction of chlorine (Cl) radical with heterocyclic saturated ether, tetrahydrofuran has been studied. The detailed reactivity and mechanism of this reaction is analyzed using hybrid density functional theory (DFT), B3LYP and BB1K methods, and aug-cc-pVTZ basis set. To explore the mechanism of the reaction of tetrahydrofuran with Cl radical, four possible sites of hydrogen atom (H) abstraction pathways in tetrahydrofuran were analyzed. The barrier height and rate constants are calculated for the four H-abstraction channels. The BB1K calculated rate constant for α-axial H-abstraction is comparable with the experimentally determined rate constant. It reflects that α-axial H-abstraction is the main degradation pathway of tetrahydrofuran with Cl radical. DFT-based reactivity descriptors are also calculated and these values describe α-axial H-abstraction as the main reaction channel.