S-S bond mesolysis in alpha,alpha'-dinaphthyl disulfide radical anion generated during gamma-radiolysis and pulse radiolysis in organic solution

A dissociation mechanism of the S-S bond in the alpha,alpha'-dinaphthyl disulfide radical anion (NpSSNp*-) in organic solution was investigated on the basis of transient absorption measurements and DFT calculations. NpSSNp*- generated during gamma-radiolysis of NpSSNp in MTHF at 77 K showed the absorption band at 430 nm, which shifted to 560 nm with an increase of the ambient temperature up to room temperature. With the aid of DFT calculations at the B3LYP/6-31G(d) level, the shift of the absorption band was interpreted in terms of molecular conformational changes of NpSSNp*- due to the elongation of the S-S bond. It was observed that NpSSNp*- dissociates into naphthylthiyl radical and thionaphtholate anion in organic solution with a first-order rate constant in the magnitude of 10(6) s-1. From Arrhenius plots of the decay rate constants of NpSSNp*- in a temperature range of 160-293 K, an activation energy for the S-S bond cleavage in NpSSNp*- in solution was determined along with a frequency factor. Based on the state energies of NpSSNp*- calculated at the B3LYP/6-31G(d) level, a Morse-like energy potential for the S-S bond cleavage of NpSSNp*- is depicted as a function of the S-S bond distance.     

Formation of quinoid fragments in vacuum-deposited poly-para-phenylene films: IR spectroscopy evidence

The structure of vacuum-deposited poly-para-phenylene (PPP) films prepared from a high-molecular-weight PPP powder has been investigated by IR spectroscopy. It has been demonstrated that in IR spectra of PPP films exhibiting intense luminescence an extremely strong band at 1375 cm⁻¹ is observed, which is not typical for currently known PPP modifications. Based on the IR spectral data, the model of formation of a PPP chain with quinoid fragments in the ground electronic state is proposed. The structure of defects that inevitably spring up during the benzenoid–quinoid transition is discussed. High intensity of the band at 1375 cm⁻¹ is associated with the change in the order of the “defect” C C bond between adjacent quinoid and benzenoid units. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1043–1052, 1998     

Electron attachment step in electron capture dissociation (ECD) and electron transfer dissociation (ETD)

We have made use of classical dynamics trajectory simultions and ab initio electronic structure calculations to estimate the cross sections with which electrons are attached (in electron capture dissociation (ECD)) or transferred (in electron transfer dissociation (ETD)) to a model system that contained both an S-S bond that is cleaved and a -NH(3)(+) positively charged site. We used a Landau-Zener-Stueckelberg curve-crossing approximation to estimate the ETD rates for electron transfer from a CH(3)(-) anion to the -NH(3)(+) Rydberg orbital or the S-S sigma* orbital. We draw conclusions about ECD from our ETD results and from known experimental electron-attachment cross sections for cations and sigma-bonds. We predict the cross section for ETD at the positive site of our model compound to be an order of magnitude larger than that for transfer to the Coulomb-stabilized S-S bond site. We also predict that, in ECD, the cross section for electron capture at the positive site will be up to 3 orders of magnitude larger than that for capture at the S-S bond site. These results seem to suggest that attachment to such positive sites should dominate in producing S-S bond cleavage in our compound. However, we also note that cleavage induced by capture at the positive site will be diminished by an amount that is related to the distance from the positive site to the S-S bond. This dimunition can render cleavage through Coulomb-assisted S-S sigma* attachment competitive for our model compound. Implications for ECD and ETD of peptides and proteins in which SS or N-C(alpha) bonds are cleaved are also discussed, and we explain that such events are most likely susceptible to Coulomb-assisted attachment, because the S-S sigma* and C=O pi* orbitals are the lowest-lying antibonding orbitals in most peptides and proteins.     

Coupled-cluster study of the electronic structure and energetics of tetrasulfur, S4

Ab initio electronic structure calculations are reported for S4. Geometric and energetic parameters are calculated using the singles and doubles coupled-cluster method, including a perturbutional correction for connected triple excitation, CCSD(T), together with systematic sequences of correlation consistent basis sets extrapolated to the complete basis set limit. The geometry for the ground state singlet C2v structure of S4 is in good agreement with the microwave structure determined for S4. There is a low-lying D2h transition state at 1.6 kcal/mol which interchanges the long S-S bond. S4 has a low-lying triplet state (3B 1u) in D2h symmetry which is 10.8 kcal/mol above the C2v singlet ground state. The S-S bond dissociation energy for S4 into two S2(3Sigma*g) molecules is predicted to be 22.8 kcal mol(-1). The S-S bond energy to form S3+S(3P) is predicted to be 64 kcal/mol.     

A novel salt bridge mechanism highlights the need for nonmobile proton conditions to promote disulfide bond cleavage in protonated peptides under low-energy collisional activation

The gas-phase fragmentation mechanisms of small models for peptides containing intermolecular disulfide links have been studied using a combination of tandem mass spectrometry experiments, isotopic labeling, structural labeling, accurate mass measurements of product ions, and theoretical calculations (at the MP2/6-311 + G(2d,p)//B3LYP/3-21G(d) level of theory). Cystine and its C-terminal derivatives were observed to fragment via a range of pathways, including loss of neutral molecules, amide bond cleavage, and S-S and C-S bond cleavages. Various mechanisms were considered to rationalize S-S and C-S bond cleavage processes, including charge directed neighboring group processes and nonmobile proton salt bridge mechanism. Three low-energy fragmentation pathways were identified from theoretical calculations on cystine N-methyl amide: (1) S-S bond cleavage dominated by a neighboring group process involving the C-terminal amide N to form either a protonated cysteine derivative or protonated sulfenyl amide product ion (44.3 kcal mol(-1)); (2) C-S bond cleavage via a salt bridge mechanism, involving abstraction of the alpha-hydrogen by the N-terminal amino group to form a protonated thiocysteine derivative (35.0 kcal mol(-1)); and (3) C-S bond cleavage via a Grob-like fragmentation process in which the nucleophilic N-terminal amino group forms a protonated dithiazolidine (57.9 kcal mol(-1)). Interestingly, C-S bond cleavage by neighboring group processes have high activation barriers (63.1 kcal mol(-1)) and are thus not expected to be accessible during low-energy CID experiments. In comparison to the energetics of simple amide bond cleavage, these S-S and C-S bond cleavage reactions are higher in energy, which helps rationalize why bond cleavage processes involving the disulfide bond are rarely observed for low-energy CID of peptides with mobile proton(s) containing intermolecular disulfide bonds. On the other hand, the absence of a mobile proton appears to "switch on" disulfide bond cleavage reactions, which can be rationalized by the salt bridge mechanism. This potentially has important ramifications in explaining the prevalence of disulfide bond cleavage in singly protonated peptides under MALDI conditions.     

Band deconvolution analysis of the absorption and magnetic circular dichroism spectral data of a planar phthalocyanine dimer

The electronic absorption and magnetic circular dichroism spectral data of a phthalocyanine dicopper complex that is deduced to be very planar and to share a common benzene ring have been studied by band deconvolution analysis. The results were compared with those of the molecular orbital (MO) calculations within the framework of the Pariser-Parr-Pople (PPP) approximation. The results of the band deconvolution analysis are in good agreement with those of the PPP calculations, allowing many bands to be reasonably assigned on the basis of the MO calculations. The validity of the PPP method for the MO calculation of large molecules is also emphasized.     

An ab initio MO study on the disulfide bond: properties concerning the characteristic S-S dihedral angle

The characteristics of disulfide groups concerning the S-S dihedral angle are represented by ab initio SCF calculations using the split-valence 6-31G(^*) basis set. It is shown that the hyperconjugation between the S-H bond and the electron pair on the other sulfur plays an important role in determining the characteristic S-S dihedral angle. The S 3d orbitals do not participate in such characteristics. The nature of the S-S bond is compared with that of the O-O bond. The S-S bond length varies largely depending on the S-S dihedral angle. This is related to the frequency-conformation correlation of the disulfide group.     

Redox properties of C6S8(n-) and C3S5(n-) (n = 0, 1, 2): stable radicals and unusual structural properties for C-S-S-C bonds

The new anionic carbon sulfides C6S10(2-) and C12S16(2-) are described and crystallographically characterized. The C12S16(2-) anion consists of two C6S8 units connected by an exceptionally long (2.157(12) A) S-S bond. In solution, C12S16(2-) exists in equilibrium with the radical C6S8(-*). The equilibrium constant for radical formation (293 K, THF) is 1.2 x 10(-4) M, as determined by optical spectroscopy at varying concentrations. Radical formation occurs through scission of the S-S bond. On the basis of variable temperature EPR spectra, the thermodynamic parameters of this process are DeltaH = +51.5 +/- 0.5 kJ x mol(-1) and DeltaS = +110 +/- 3 J x mol(-1) x K(-1). C6S10(2-) is an oxidation product of C3S5(2-) and consists of two C3S5 units connected by an S-S bond. The S-S bond length (2.135(4) A) is long, and the CS-SC torsion angle is unusually acute (52.1 degrees ), which is attributed to an attractive interaction between C3S2 rings. The oxidation of (Me4N)2C3S5 occurs at -0.90 V vs Fc+/Fc in MeCN, being further oxidized at -0.22 V. The similarity of the cyclic voltammogram of (Me4N)2C6S10 to that of (Me4N)2C3S5 indicates that C6S10(2-) is the initial oxidation product of C3S5(2-).     

Ligand structural effects on Cu2S2 bonding and reactivity in side-on disulfido-bridged dicopper complexes

To assess supporting ligand effects on S-S bond activation, a series of [Cu2(mu-eta2:eta2-S2)]2+ complexes supported by various beta-diketiminate or anilido-imine ligands (L) were synthesized via the reaction of Cu(I) precursors LCu(CH(3)CN) with S8. For the cases where L = beta-diketiminate, the syntheses were complicated by formation of clusters [Cu(SR)]4, where SR represents the ligand functionalized by sulfur at the central methine position. The [Cu2(mu-eta2:eta2-S2)]2+ products were characterized by X-ray crystallography and electronic absorption and resonance Raman spectroscopy. Correlations among the Cu-S, Cu-Cu, and S-S distances and the nu(S-S) values were observed and interpreted within the framework of a previously described bonding picture (Chen, P.; Fujisawa, K.; Helton, M. E.; Karlin, K. D.; Solomon, E. I. J. Am. Chem. Soc. 2003, 125, 6394). Comparison of these data to those for other relevant species revealed a remarkable degree of S-S bond activation in the compounds supported by the beta-diketiminate and anilido-imine ligands, which through strong electron donation increase backbonding from the copper ions into the S-S sigma* orbital and cause S-S bond weakening. Reactions of one of the complexes supported by an anilido-imine ligand with PPh(3) and xylyl isocyanide were explored, revealing facile transfer of sulfur to PPh(3) but only displacement of sulfur to yield a LCu(I)-CNAr (Ar = xylyl) complex with the isocyanide.     

Vibrational spectroscopic studies of mesna and dimesna

Raman, and infrared spectra of mesna and dimesna have been collected in the present spectroscopic studies. Based on the group frequencies, relative intensities and Raman depolarization measurements, some vibrational assignments have been suggested. For both mesna and dimesna, at least two rotational conformers have been identified. Adsorption behavior was investigated from the recorded surface-enhanced Raman scattering (SERS) spectra. It was found that both mesna and dimesna adsorbed as thiolate on silver sol particles with the cleavage of the S-H bond in mesna and the S-S bond in dimesna. For the adsorbed thiolate, two conformers existed in the adsorption state.     

Accounting for the differences in the structures and relative energies of the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I4 2+, the Se-I pi-bonded Se2I4 2+, and their higher-energy isomers by AIM, MO, NBO, and VB methodologies

The bonding in the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I42+ (three sigma + two pi bonds), the Se-I pi-bonded Se2I42+ (four sigma + one pi bonds), and their higher-energy isomers have been studied using modern DFT and ab initio calculations and theoretical analysis methods: atoms in molecules (AIM), molecular orbital (MO), natural bond orbital (NBO), and valence bond (VB) analyses, giving their relative energies, theoretical bond orders, and atomic charges. The aim of this work was to seek theory-based answers to four main questions: (1) Are the previously proposed simple pi*-pi* bonding models valid for S2I42+ and Se2I42+? (2) What accounts for the difference in the structures of S2I42+ and Se2I42+? (3) Why are the classically bonded isolobal P2I4 and As2I4 structures not adopted? (4) Is the high experimentally observed S-S bond order supported by theoretical bond orders, and how does it relate to high bond orders between other heavier main group elements? The AIM analysis confirmed the high bond orders and established that the weak bonds observed in S2I42+ and Se2I42+ are real and the bonding in these cations is covalent in nature. The full MO analysis confirmed that S2I42+ contains three sigma and two pi bonds, that the positive charge is essentially equally distributed over all atoms, that the bonding between S2 and two I2+ units in S2I42+ is best described by two mutually perpendicular 4c2e pi*-pi* bonds, and that in Se2I42+, two SeI2+ moieties are joined by a 6c2e pi*-pi* bond, both in agreement with previously suggested models. The VB treatment provided a complementary approach to MO analysis and provided insight how the formation of the weak bonds affects the other bonds. The NBO analysis and the calculated AIM charges showed that the minimization of the electrostatic repulsion between EI2+ units (E = S, Se) and the delocalization of the positive charge are the main factors that explain why the nonclassical structures are favored for S2I42+ and Se2I42+. The difference in the structures of S2I42+ and Se2I42+ is related to the high strength of the S-S pi bond compared to the weak S-I sigma bond and the additional stabilization from increased delocalization of positive charge in the structure of S2I42+ compared to the structure of Se2I42+. The investigation of the E2X42+ series (E = S, Se, Te; X = Cl, Br, I) revealed that only S2I42+ adopts the highly np pi-np pi (n > or = 3)-bonded structure, while all other dications favor the pi-bonded Se2I42+ structure. Theoretical bond order calculations for S2I42+ confirm the previously presented experimentally based bond orders for S-S (2.1-2.3) and I-I (1.3-1.5) bonds. The S-S bond is determined to have the highest reported S-S bond order in an isolated compound and has a bond order that is either similar to or slightly less than the Si-Si bond order in the proposed triply bonded [(Me3Si)2CH]2(iPr)SiSi triple bond SiSi(iPr)[CH(SiMe3)2]2 depending on the definition of bond orders used.     

Crystal structures of triazine-3-thione derivatives by reaction with copper and cobalt salts

The reaction of 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione L1H2OCH3 with copper(II) chloride leads to the formation of an organic molecule L2 containing two triazine rings linked by a new S-S bond. A binuclear copper(II) complex, 1, containing L1 is also isolated. The reaction of L1H2OCH3 with copper(I) chloride yields a hexanuclear cluster of copper(I), 2, in which the copper atoms form a distorted octahedron with the ligand L1 acting as an NS chelate and sulfur bridge, giving to the copper ion a trigonal geometry by one N and two S atoms. In any reaction of the disulfide L2 with metal salts, complexes containing this molecule are isolated. Reactions with copper(I) and copper(II) chloride and nickel(II) and cadmium(II) nitrate produce the S-S bond cleavage, giving complexes containing the triazine L1 behaving as the NS anion, which show spectroscopic characteristics identical with those formed by reaction with L1H2OCH3. However, the reaction with cobalt(II) nitrate gives a low-spin octahedral cobalt(III) complex, in which an asymmetric rupture of the disulfide L2 has been produced, giving an unexpected complex with a new ligand and keeping the S-S bond.     

The role of excited Rydberg States in electron transfer dissociation

Ab initio electronic structure methods are used to estimate the cross sections for electron transfer from donor anions having electron binding energies ranging from 0.001 to 0.6 eV to each of three sites in a model disulfide-linked molecular cation. The three sites are (1) the S-S sigma(*) orbital to which electron attachment is rendered exothermic by Coulomb stabilization from the nearby positive site, (2) the ground Rydberg orbital of the -NH(3)(+) site, and (3) excited Rydberg orbitals of the same -NH(3)(+) site. It is found that attachment to the ground Rydberg orbital has a somewhat higher cross section than attachment to either the sigma orbital or the excited Rydberg orbital. However, it is through attachment either to the sigma(*) orbital or to certain excited Rydberg orbitals that cleavage of the S-S bond is most likely to occur. Attachment to the sigma(*) orbital causes prompt cleavage because the sigma energy surface is repulsive (except at very long range). Attachment to the ground or excited Rydberg state causes the S-S bond to rupture only once a through-bond electron transfer from the Rydberg orbital to the S-S sigma(*) orbital takes place. For the ground Rydberg state, this transfer requires surmounting an approximately 0.4 eV barrier that renders the S-S bond cleavage rate slow. However, for the excited Rydberg state, the intramolecular electron transfer has a much smaller barrier and is prompt.     

非晶硅短程序与电子结构关系的量子化学研究

本支通过对Si_(29)无规网络原子簇模型的CNDO计算,探讨了非晶硅(a-Si)结构短程序对其电子态密度(DOS)分布的影响。结果表明,在与实验原子径向分布函数(RDF)基本相同的条件下,a-Si模型中的键角和二面角是影响电子态密度分布的主要参数。     

CNDO/2 and MINDO/2 energy band structures of some homopolynucleotides

The all-valence electron band structures of the periodic DNA models polyC, polyT, and polyA have been calculated with the aid of the CNDO /2 and MINDO /2 crystal orbital (CO ) method. According to the obtained results the valence and conduction bands are always of π type. The widths of the bands are usually larger in the CNDO case, than those obtained for the same systems in the PPP CO approximation. On the other hand the MINDO results show similar widths as the PPP ones. The forbidden bandwidths are by 3–4 eV larger in the CNDO /2 case, than in the PPP one, while the MINDO /2 CO method has resulted in similar gaps like the PPP calculation.     

Determination of thiocarbamyl sulphenamides, thiuram disulphides and dibenzothiazyl disulphide by amperometric titration

An amperometric method for the determination of thiocarbamyl sulphonamides has been developed, based on the cleavage of the S-N bond by hydriodic acid. The method can also be applied for the cleavage of the S-S bond in thiuram disulphides and dibenzothiazyl disulphide, and thus provides a useful means for the estimation of these compounds as well.     

Bis(trifluoroaceto) disulfide (CF3C(O)OSSOC(O)CF3): a HeI photoelectron spectroscopy and theoretical study

Bis(trifluoroaceto) disulfide CF(3)C(O)OSSOC(O)CF(3) was prepared and studied by Raman, photoelectron spectroscopy (PES), and theoretical calculations. This molecule exhibits gauche conformation with both C=O groups cis to the S-S bond; the structure of the OSSO moiety is characterized by dihedral angle delta(OSSO) = -95.1 degrees due to the sulfur-sulfur lone pair interactions. The contracted S-S bond (1.979 Angstroms) and relatively high rotational barrier (19.29 kcal mol(-1) at the B3LYP/6-31G level) of the delta(OSSO) indicate the partial resonance-induced double bond character in this molecule. After ionization, the ground cationic-radical form of CF(3)C(O)OSSOC(O)CF(3)(*+) adopts a trans planar main-atom structure (delta(OSSO) = 180 degrees and delta(OCOS) = 0 degrees ) with C(2)(h) symmetry. The S-S bond elongates to 2.054 Angstroms, while the S-O bond shortens from 1.755 Angstroms in neutral form to 1.684 Angstroms in its corresponding cationic-radical form. The adiabatic ionization energy of 9.91 eV was obtained accordingly. The first two HOMOs correspond to the electrons mainly localized on the sulfur 3p lone pair MOs: 3ppi {36a (n(A)(S))](-1) and 3ppi [35b (n(B)(S), n(B)(O(C)(=)(O)))](-1), with an experimental energy separation of 0.16 eV. The first vertical ionization energy is determined to be 10.81 eV.     

Synthesis of Novel High Energy Polyaniline Derivative Containing S-S Bond in Six-membered Cycle

A novel conducting polymer as new class of high energy storage material, [1,2] which has one six-membered cycle containing S-S bond in the moiety of aniline was synthesized. The polymer had enhanced redox progress due to an intramolecular electrocatalytic effect of polyaniline on S-S bond. The polymer has some advantages because of its high theoretical specific energy and fast kinetics when used in lithium batteries. The most promised advantage of it is that the intramolecular cleavage and recombination of the S-S bond improve the cyclicability greatly.     

Mechanistic study of palladium catalyzed S-S and Se-Se bonds addition to alkynes

The mechanistic study of palladium catalyzed S-S and Se-Se bonds addition to alkynes revealed the involvement of dinuclear transition metal complexes in the catalytic cycle. Coordination of alkyne to dinuclear transition metal complex was found to be the rate determining step of the reaction. An unusual phosphine ligand effect increasing the yield of addition reaction was found in the studied system. A new synthetic procedure was developed to perform the catalytic reaction using easily available Pd(II) complex. The scope of the reaction and the reactivity of S-S and Se-Se bonds toward alkynes were investigated. The X-ray structure of the product of S-S bond addition reaction showed favorable geometry for the possible application as a chelate ligand.