Contribution of the lipophilic buffer to chiral recognition under reversed-phase conditions

Summary A lipophilic buffered aqueous mobile phase, without organic modifier, was used for the high performance liquid chromatographic enantioseparation of D,L-lactic acid on a Merck ChiraSpher (250 mm×4 mm i.d.) column in which the chiral selector is poly(N-acryloyl-S-phenylalanine ethyl ester) bonded to a spherical silica particle. The lipophilicity of the buffer was achieved by addition of triethylammonium phosphate, the ‘ethyl’ apolar chains of which dynamically modified the ChiraSpher stationary phase and increased its hydrophobic character. The ion-paired (cethyltrimethylammonium bromide) analyte enantioseparation was realized by hydrogen-bonding and dipole-dipole complexation on the ChiraSpher stationary phase, superimposed on simultaneous reversed-phase partitioning. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Some chemical properties of (arene)nonacarbonyltetracobalt complexes and the preparation of (arene)octacarbonyltetracobalt trialkylphosphites

In reactions of Co₄(CO)₉(arene) with carbon monoxide, phosphines and acetylenes, displacement of the arene takes place and known derivatives of Co₄(CO)₁₂ and Co₂(CO)₈ are formed. With phosphites, however, displacement of one carbon monoxide can be achieved, to give Co₄(CO)₈(arene)P(OR)₃. The same type of complexes can also be prepared by treatment of Co₄(CO)₁₁P(OR)₃ with arenes.     

Mercury(II) Compounds with 1,3-Benzothiazole-2-thione. Spectral, Thermal, and Crystal Structure Studies

Mercury(II) halides, HgX₂ (X = Cl^–, Br^–, I^–) react with 1,3-benzothiazole-2-thione (btztH) in methanol solutions giving the HgX₂(btztH) and HgX₂(btztH)₂ types of compounds. Mercury(II) acetate gives the thiolato compound Hg(btzt)₂ because of the deprotonation of btztH. Hg(btzt)₂ reacts with 2,2-bipyridine (bipy) giving a 1:1 complex. IR, ¹H, and ¹³C NMR spectral studies indicate that btztH acts as a monodenatate ligand through the S thione donor atom in all complexes. The X-ray crystal structure determinations of [HgI₂(btztH)]₂, HgBr₂(btztH)₂, Hg(btzt)₂, and Hg(btzt)₂(bipy) have been carried out revealing tetrahedrally coordinated mercury atom in [HgI₂(btztH)]₂ and HgBr₂(btztH)₂, while in Hg(btzt)₂(bipy) 2 + 2 coordination is achieved through strong Hg (N(bipy) contacts. A linear coordination in Hg(btzt)₂ is not affected by the Hg N contacts, which are longer than in Hg(btzt)₂(bipy), but still shorter than the van der Waals sum of mercury and nitrogen covalent radii. [HgI₂(btztH)]₂ exists as centrosymmetrical dimer with a Hg₂I₂ bridging core. The dimeric molecules are linked by the intermolecular hydrogen bonds between the terminal iodine atom and the NH group [3.63(1) Å] into infinite chains along the z-axis. There are N–H Br(bridging) intermolecular hydrogen bonds in HgBr₂(btztH)₂ joining molecules into endless chains along the x-axis. The Br(bridging) atom acts as double proton acceptor and two NH groups as proton donors [NH Br(bridging) 3.278(9) and 3.338(7) Å]. The mercury to sulfur and mercury to halogen bond distances in [HgI₂(btztH)]₂ and HgBr₂(btztH)₂ are discussed in relation to the analogous compounds, revealing strong influence of hydrogen bonds on their relative strengths as well as crystal packing requirements of the ligand. The sulfur and halogen atoms are more tightly bound to mercury implicating severe distortion of the coordination polyhedron in the structures in which they do not take part in hydrogen bonds formation. The influence of steric requirements of the ligands in Hg(btzt)₂ and Hg(btzt)₂(bipy) on the distortion of the mercury coordination polyhedra accompanied with the relative strength of Hg N contacts is considered.     

ESI‐MS studies of the non‐covalent interactions between biologically important metal ions and N‐sulfonylcytosine derivatives

The aim of this report is to present the electrospray ionization mass spectrometry results of the non‐covalent interaction of two biologically active ligands, N‐1 ‐ (p‐toluenesulfonyl)cytosine, 1‐TsC, 1 and N‐1 ‐ methanesulfonylcytosine, 1‐MsC, 2 and their Cu(II) complexes Cu(1‐TsC‐N3)₂Cl₂, 3 and Cu(1‐MsC‐N3)₂Cl₂ and 4 with biologically important cations: Na⁺, K⁺, Ca²⁺, Mg²⁺ and Zn²⁺. The formation of various complex metal ions was observed. The alkali metals Na⁺ and K⁺ formed clusters because of electrostatic interactions. Ca²⁺ and Mg²⁺ salts produced the tris ligand and mixed ligand complexes. The interaction of Zn²⁺ with 1–4 produced monometal and dimetal Zn²⁺ complexes as a result of the affinity of Zn²⁺ ions toward both O and N atoms. Copyright © 2016 John Wiley & Sons, Ltd.     

A new cytosine-copper paramagnetic complex spectroscopic study

Two different copper complexes with cytosine molecules are formed in the process of crystal growth from the aqueous solution with traces of copper. One of them is diamagnetic, turning into paramagnetic upon ionizing irradiation (complex I). The other, the subject of the present study, is paramagnetic (complex II) as prepared. For complex II, EPR spectra demonstrate that the copper ion is coordinated with one nitrogen atom and three oxygen atoms. On the basis of the detailed EPR spectroscopic analysis and quantum-chemical calculations (in the DFT approach) the model of the complex has been proposed. Both experimental data and the theoretical results support the model with the copper atom, located between the two cytosine ribbons, ligated to a nitrogen and an oxygen atom from two opposing cytosine molecules and two oxygen atoms from water molecules. For complex II the Raman spectra demonstrated concerted restructuring of the hydrogen bonding in the cytosine crystal matrix upon insertion of copper ions.     

The Langlands classification for non-connectedp-adic groups

We give the Langlands classification for a non-connected reductive quasisplitp-adic groupG, under the assumption thatG/G ⁰ is abelian (here,G ⁰ denotes the connected component of the identity ofG). The Langlands classification for non-connected groups is an extension of the Langlands classification from the connected case.     

A 1:2 complex of mercury(II) chloride with 1,3‐imidazole‐2‐thione

The Hg atom in the title monomeric complex, di­chloro­bis(3‐imidazolium‐2‐thiol­ato‐S)­mercury(II), [HgCl₂(C₃H₄N₂S)₂], is four‐coordinate having an irregular tetrahedral geometry composed of two Cl atoms [Hg—Cl 2.622 (2) and 2.663 (2) Å] and two thione S atoms [Hg—S 2.445 (2) and 2.462 (2) Å]. The monodentate thione ligand adopts a zwitterionic form and exists as the 3‐imidazolium‐2‐thiol­ate ion. The bond angle S1—Hg—S2 of 130.87 (8)° has the greatest deviation from ideal tetrahedral geometry. Intermolecular hydrogen bonds between two of the four N—H groups and one of the Cl atoms [3.232 (8) and 3.238 (7) Å] stabilize the crystal structure, while the other two N—H groups contribute through the formation of N—H?Cl intramolecular hydrogen bonds with the other Cl atom [3.121 (7) and 3.188 (7) Å].     

The Search for Tricyanomethane (Cyanoform)

Although listed in organic chemistry textbooks as one of the strongest carbon acids, and in spite of more than a hundred years of attempts to prepare the compound, tricyanomethane (cyanoform) has resisted isolation and characterization, either as the carbon‐acid 1 or as the dicyanoketenimine tautomer 2 . Only in the vapor phase at very low pressure has the compound been identified from its microwave spectrum. Here we review and partially repeat the preparative work. With the aid of spectroscopic and diffraction methods (including powder diffraction) we have identified some of the products obtained as: hydronium tricyanomethanide ( 3 ), (Z)‐3‐amino‐2‐cyano‐3‐iminoacrylimide ( 4 ), a co‐crystal of 4 with sulfuric acid (or corresponding iminium salt), and an addition product of 2 with hydrochloric acid ( 5 / 6 ). Quantum‐mechanical calculations at the MP2/6‐311++g(2d,2p) level have been made to assess the relative energies of some of the molecules involved.     

Quadrant analysis of persistent spatial velocity perturbations over square-bar roughness

We explore a new application of the quadrant method in the context of the double-averaged Navier–Stokes equations for studying open channel flow near rough beds. Quadrant analysis is applied to spatial disturbances of time-averaged velocity components, using the experimental data from flow over two-dimensional regular transverse square-bar roughness. The spatial velocity disturbances change periodically performing a full cycle over a single roughness element, so that the quadrant diagrams are regular closed orbits. A colour code is used to produce a quadrant map of the flow cross-section, which reveals contributions from each quadrant to the time-averaged momentum transfer.