In search of CS2(H2O)(n=1-4) clusters

Gaussian-3 and MP2/aug-cc-pVnZ methods have been used to calculate geometries and thermochemistry of CS(2)(H2O)n, where n=1-4. An extensive molecular dynamics search followed by optimization using these two methods located two dimers, six trimers, six tetramers, and two pentamers. The MP2/aug-cc-pVDZ structure matched best with the experimental result for the CS(2)(H2O) dimer, showing that diffuse functions are necessary to model the interactions found in this complex. For larger CS(2)(H2O)n clusters, the MP2/aug-cc-pVDZ minima are significantly different from the MP2(full)6-31G* structures, revealing that the G3 model chemistry is not suitable for investigation of sulfur containing van der Waals complexes. Based on the MP2/aug-cc-pVTZ free energies, the concentration of saturated water in the atmosphere and the average amount of CS(2) in the atmosphere, the concentrations of these clusters are predicted to be on the order of 10(5) CS(2)(H2O) clusters.cm(-3) and 10(2) CS(2)(H2O)(2) clusters.cm(-3) at 298.15 K. The MP2/aug-cc-pVDZ scaled harmonic and anharmonic frequencies of the most abundant dimer cluster at 298 K are presented, along with the MP2/aug-cc-pVDZ scaled harmonic frequencies for the CS(2)(H(2)O)(n) structures predicted to be present in a low-temperature molecular beam experiment.     

Electronic structures of tris(dioxolene)chromium and tris(dithiolene)chromium complexes of the electron-transfer series [Cr(dioxolene)(3)](z) and [Cr(dithiolene)(3)](z) (z = 0, 1-, 2-, 3-). A combined experimental and density functional theoretical study

From the reaction mixture of 3,6-di-tert-butylcatechol, H2[3,6L(cat)], [CrCl3(thf)3], and NEt3 in CH3CN in the presence of air, the neutral complex [CrIII(3,6L*(sq))3] (S = 0) (1) was isolated. Reduction of 1 with [Co(Cp)2] in CH2Cl2 yielded microcrystals of [Co(Cp)2][CrIII(3,6L*(sq))2(3,6L(cat))] (S = 1/2) (2) where (3,6L*(sq)(1-) is the pi-radical monoanionic o-semiquinonate of the catecholate dianion (3,6Lcat)(2-). Electrochemistry demonstrated that both species are members of the electron-transfer series [Cr(3,6LO,O)]z (z = 0, 1-, 2-, 3-). The corresponding tris(benzo-1,2-dithiolato)chromium complex [N(n-Bu)4][CrIII(3,5L*S,S)2(3,5LS,S)] (S = 1/2) (3) has also been isolated; (3,5LS,S)(2-) represents the closed-shell dianion 3,5-di-tert-butylbenzene-1,2-dithiolate(2-), and (3,5L*S,S)(1-) is its monoanionic pi radical. Complex 3 is a member of the electron-transfer series [Cr(3,5L(S,S))3]z (z = 0, 1-, 2-, 3-). It is shown by Cr K-edge and S K-edge X-ray absorption, UV-vis, and EPR spectroscopies, as well as X-ray crystallography, of 1 and 3 that the oxidation state of the central Cr ion in each member of both electron-transfer series remains the same (+III) and that all redox processes are ligand-based. These experimental results have been corroborated by broken symmetry density functional theoretical calculations by using the B3LYP functional.     

Electrosynthesis and characterization of 1,2-dibenzyl C60: a revisit

A reinvestigation of the reaction between C60(2-) and benzyl bromide in benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) has shown that there are more reaction products than previously reported. Use of a silica rather than a "Buckyclutcher I" column for HPLC purification led to isolation of two previously unattained products in the reaction mixture, one of which was identified as 1,2-(PhCH2)2C60 by UV-vis and NMR . The earlier incorrectly assigned 1,2-(PhCH2)2C60 was identified as the methanofullerene C61HPh by X-ray single-crystal diffraction. The electrochemistry of genuine 1,2-(PhCH2)2C60 shows that its first reduction potential in PhCN containing 0.1 M TBAP is cathodically shifted by 100 mV with respect to E1/2 for reduction of 1,4-(PhCH2)2C60, indicating that the addition pattern significantly affects the electrochemistry of derivatized C60. Visible and near-IR spectra of the monoanion and dianion of 1,2-(PhCH2)2C60 are also reported.     

SmI(2)-promoted radical addition reactions with N-(2-Indolylacyl)oxazolidinones: synthesis of bisindole compounds

The treatment of N-acyl oxazolidinones of N-benzyl 2-indolecarboxylic acids varying in the substitution pattern of the indole ring with samarium diiodide at -78 degrees C led to the formation of two indole dimer products. The major product isolated in yields from 55 to 59% represents an unsymmetrical dimer arising from 1,4-addition to the 2-indolecarboxylic acid derivative of a possible ketyl-type radical anion intermediate originating from the reduction of the exocyclic carbonyl group of the N-acyl oxazolidinone. The minor dimer, represented by a symmetrical diketone, was produced in yields ranging from 11 to 23%. Even in the presence of an alpha,beta-unsaturated amide, dimerization was the preferred pathway rather than the formation of a gamma-keto amide. Upon treatment with acid, the unsymmetrical indole dimer cyclized to form a diindolequinone. Finally, the N-acyl oxazolidinones of pyrrole-2-carboxylic acid and 3-indolecarboxylic acid preferred in both cases to undergo C-C bond formation with an acrylamide in the presence of SmI2 rather than dimerization.     

Organocatalytic enantioselective nucleophilic vinylic substitution by alpha-substituted-alpha-cyanoacetates under phase-transfer conditions

The organocatalytic enantioselective formation of vinyl-substituted all-carbon quaternary stereocenters via nucleophilic vinylic substitution by alpha-substituted-alpha-cyanoacetates is presented. The reaction proceeds well for different alpha-substituted-alpha-cyanoacetates and beta-chloroalkenones using a dimeric cinchona alkaloid phase-transfer catalyst giving the products in good yield and with enantioselectivities up to 98% ee.     

Ring-opening and ring-closing reactions of a shikimic acid-derived substrate leading to diverse small molecules

An epoxide derived from (-)-shikimic acid was attached to a solid support and used to synthesize over 5000 diverse small molecules. Key transformations include a Lewis acid-catalyzed epoxide opening with amines and an intramolecular Heck reaction with aryl iodides. Compounds derived from this pathway were printed onto small-molecule microarrays and screened for binding to proteins. Compounds that bound to Aurora A kinase were characterized using surface plasmon resonance.     

Interior Regularity Criteria for Suitable Weak Solutions of the Navier-Stokes Equations

We present new interior regularity criteria for suitable weak solutions of the 3-D Navier-Stokes equations: a suitable weak solution is regular near an interior point z if either the scaled -norm of the velocity with 3/p + 2/q ≤ 2, 1 ≤ q ≤ ∞, or the -norm of the vorticity with 3/p + 2/q ≤ 3, 1 ≤ q < ∞, or the -norm of the gradient of the vorticity with 3/p + 2/q ≤ 4, 1 ≤ q, 1 ≤ p, is sufficiently small near z.     

On particle multiplicities in three-jet events

A thorough verification of the distinct differences in the properties of quark and gluon jets is considered as one of the most instructive tests of the basic ideas of QCD. In the real life experiments such a comparison appears to be quite a delicate task and various subtle issues require further theoretical efforts. In this paper we discuss in detail the possibility to extract the theoretically adequate information from the particle multiplicity patterns in three-jet events in annihilation. Received: 8 June 1999 / Published online: 14 October 1999     

Molecular complexes of 3-amino-1,2,4-triazole: The crystal structure of 3-amino-1,2,4-triazolium 5-nitrofuran-d2-carboxylate

3-Amino-1,2,4-triazolium (3-AT) 5-nitrofuran-2-carboxylate has been prepared and its x-ray crystal structure reported (a = 12.363(3) Å, b = 12.5720(10) Å, c = 12.8550(10) Å, Pbca, orthorhombic, Z = 8, and D _c = 1.604 mg m^–3). The solid-state packing of this organic acid-base salt consists of a three-dimensional hydrogen-bonded network which exhibits a cage-like repeat unit involving both the N(2)–H and N(4)–H sites of 3-AT. A review of five such structures reveals that in all cases the carboxylate groups interact with either of these sites [and the N(31)H₂] and form a R ² ₂(8) graph set interaction. Analysis of all 3-AT complexes which form this interaction reveals that the hydrogen-bonding distances between the non-hydrogen atoms are not equal [av. 2.712(5) Å and 2.897(5) Å], with the shorter distance being the interaction between the heterocyclic nitrogen and the corresponding carboxylate oxygen. Furthermore, a review of the interactive modes of all 3-AT adducts has been undertaken.