Does dinitrogen hydrogenation follow different mechanisms for [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) and {[PhP(CH2SiMe2NSiMe2CH2)PPh]Zr}2(mu2,eta2,eta2-N2) complexes? A computational study

The mechanisms of dinitrogen hydrogenation by two different complexes--[(eta(5)-C(5)Me(4)H)(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)), synthesized by Chirik and co-workers [Nature 2004, 427, 527], and {[P(2)N(2)]Zr}(2)(mu(2),eta(2),eta(2)-N(2)), where P(2)N(2) = PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh, synthesized by Fryzuk and co-workers [Science 1997, 275, 1445]--are compared with density functional theory calculations. The former complex is experimentally known to be capable of adding more than one H(2) molecule to the side-on coordinated N(2) molecule, while the latter does not add more than one H(2). We have shown that the observed difference in the reactivity of these dizirconium complexes is caused by the fact that the former ligand environment is more rigid than the latter. As a result, the addition of the first H(2) molecule leads to two different products: a non-H-bridged intermediate for the Chirik-type complex and a H-bridged intermediate for the Fryzuk-type complex. The non-H-bridged intermediate requires a smaller energy barrier for the second H(2) addition than the H-bridged intermediate. We have also examined the effect of different numbers of methyl substituents in [(eta(5)-C(5)Me(n)H(5)(-)(n))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) for n = 0, 4, and 5 (n = 5 is hypothetical) and [(eta(5)-C(5)H(2)-1,2,4-Me(3))(eta(5)-C(5)Me(5))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) and have shown that all complexes of this type would follow a similar H(2) addition mechanism. We have also performed an extensive analysis on the factors (side-on coordination of N(2) to two Zr centers, availability of the frontier orbitals with appropriate symmetry, and inflexibility of the catalyst ligand environment) that are required for successful hydrogenation of the coordinated dinitrogen.     

Tetrakis-acridinyl peptide: distance dependence of photoinduced electron transfer in deoxyribonucleic acid assemblies

A simple determination method for halogens (Cl, Br, and I) in plant samples using inductively coupled plasma-mass spectrometry (ICP-MS) was developed. In order to extract these halogens into aqueous solution, a leaching step with tetramethyl ammonium hydroxide (TMAH) under mild conditions was carried out, i.e. a 0.1-g dried sample was left overnight (ca. 12 h) in contact with 1 mL of 25% TMAH in a small PFA vial at 60 °C. Then the sample was transferred to a 50-mL centrifuge tube and diluted to 50 mL with deionised water. After centrifugation, halogens in the supernatant were determined by ICP-MS. When standard reference materials were measured by the method, the data were within the 95% confidence range of the certified values. The results also agreed well with the values obtained by neutron activation analysis with correlation factor r > 0.99.     

Origin of the linear relationship between CH2/NH/O-SWNT reaction energies and sidewall curvature: armchair nanotubes

The origin of the linear relationship between the reaction energy of the CH2/NH/O exo and endo additions to armchair (n, n) single-walled carbon nanotubes (SWNTs) and the inverse tube diameter (1/d) measuring sidewall curvature was elucidated using density functional theory and density functional tight binding methods for finite-size SWNT models with n = 3, 4, ..., 13. A nearly perfect linear relationship between DeltaE and 1/d all through exohedral (positive curvature) and endohedral (negative curvature) additions is due to cancellation between the quadratic contributions of the SWNT deformation energy and the interaction energy (INT) between the deformed SWNT and CH2/NH/O adducts. Energy decomposition analysis shows that the quadratic contributions in electrostatic, exchange, and orbital terms mostly cancel each other, making INT weakly quadratic, and that the linear 1/d dependence of INT, and therefore of DeltaE, is a reflection of the 1/d dependence of the back-donative orbital interaction of b1 symmetry from the occupied CH2/NH/O p pi orbital to the vacant C=C pi* LUMO of the SWNT. We also discuss the origin of the two isomers (open and three-membered ring) of the exohedral addition product and explain the behavior of their associated minima on the C-C potential energy surfaces with changing d.     

An experimental and theoretical study of ring closing dynamics in HN3

We report on an H(D)-atom Rydberg tagging experiment for H(D)N(3) photolysis providing detailed dynamical information on the wavelength dependence of the H(D) + N(3) channel. We observe subtle yet striking changes in the photochemical dynamics as the photolysis energy passes through approximately 5.6 eV. In addition to producing linear azide with an average of approximately 40% of available energy appearing as translation, a second H(D)-atom producing channel grows in above this energy releasing only about 15%. An observed (inverse) isotope effect suggests that statistical decomposition on S(0) is unimportant. High level ab initio quantum chemical calculations reveal a transition state to cyclization of the N(3) moiety in H(D)N(3) on the first excited singlet (S(1)) surface that is close in energy to the experimentally observed threshold energy for this "slow channel". Furthermore, the translational energy release of the "slow channel" is energetically consistent with cyclic-N(3) formation. This work provides the clearest presently available insights into how ring closure can occur in azide photochemistry.     

Synthesis of beta-analogues of C-mannosyltryptophan, a novel C-glycosylamino acid found in proteins

alpha-C-Mannosyltryptophan (alpha-C-Man-Trp) has been found to be a novel post-translational modification of tryptophan found from some biologically important glycoproteins. In order to analyze the biological functions of alpha-C-Man-Trp, we have developed an efficient synthetic strategy for alpha-C-Man-Trp and its glucose and galactose analogues, starting from alpha-C-glycosidation of the corresponding hexapyranoside derivatives with tinacetylene. According to the synthetic routes, we describe here syntheses of beta-anomers of C-Man-Trp, and its glucose and galactose analogues from the corresponding beta-C-glycosylacetylenes. During this study, we have developed a highly stereocontrolled synthesis of beta-C-mannosylacetylene that is required for the synthesis of beta-C-Man-Trp, while the precedented method gave an anomeric mixture of the C-mannosylacetylene. The synthetic C-Man-Trp and its analogues were analyzed by HPLC.     

Raman spectroscopic study on the hydration structures of tetraethylammonium cation in water

Conformational changes of tetraethylammonium ion (Et4N+) in aqueous solution have been studied by Raman spectroscopy as functions of pressure and concentration. The difference in the partial molar volume (Delta V(tg x tg-->tt x tt)) between the trans-gauche x trans-gauche (tg x tg) and trans-trans x trans-trans (tt x tt) conformers of Et4N+ ion has been calculated from the pressure dependence of the relative Raman intensity ratio between the conformers. We discuss about the Delta V(tg x tg-->tt x tt) with two contributions from the molecular and hydration volumes. Delta V(tg x tg-->tt x tt) is found to be negative, and this is mainly due to the large molecular volume contribution. The value of Delta V(tg x tg-->tt x tt) becomes smaller with increasing R probably due to the hydration volume contribution. In view of the pressure and concentration dependences, the water molecules around Et4N+ ions at R = 19 (R= moles of water/moles of salt) mainly form the hydrophobic hydration. The hydrophobic hydration may prefer the tt x tt conformer to the tg x tg conformer. On the other hand, the hydration structure at R = 4 no longer forms the hydrophobic hydration and changes to another type of hydration, where the medium H-bond component is the dominant species. The increase of the ion-ion interactions with decreasing R induces large fractions of the tg x tg conformer.     

Synthesis and properties of trefoil-shaped tris(hexadehydrotribenzo[12]annulene) and tris(tetradehydrotribenzo[12]annulene)

[reaction: see text] Trefoil-shaped tris(hexadehydrotribenzo[12]annulene) possessing a substructure of the ultimate two-dimensional C(sp)-C(sp(2)) network, graphyne, and the related tris(tetradehydrotribenzo[12]annulene) were synthesized, and their ground- and excited-state properties were investigated.     

exo-selective asymmetric Diels-Alder reaction catalyzed by diamine salts as organocatalysts

[reaction: see text] A novel binaphthyl-based diamine (R)-2 was designed and synthesized. A protonic acid-(R)-2 salt catalyst has the advantage of exhibiting unprecedented high exo selectivity in the asymmetric Diels-Alder reaction of alpha,beta-unsaturated aldehydes. For instance, the reaction between cinnamaldehyde and cyclopentadiene in the presence of 12 mol % of binaphthyl-based diamine (R)-2 and 10 mol % of p-TsOH.H(2)O in alpha,alpha,alpha-trifluorotoluene at -20 degrees C gave the corresponding exo cycloadduct with 92% ee as a major diastereomer (exo/endo = 13/1).     

Total synthesis of (+)-lasonolide A

[structure: see text]. An enantiocontrolled total synthesis of (+)-lasonolide A has been accomplished by using the sequential cross metathesis and macrolactonization for the key assembly of the 20-membered polyene macrolide core of the natural product.