Chiral conformations induced by cyclodextrin

Studies of chiroptical properties need separation or at least enrichment of enantiomers. The separation is difficult with chiral conformers of molecules with very low barriers of internal rotation. However, in association with cyclodextrin, these labile molecules can exhibit a strong Cotton effect in solution: one chiral conformer is favoured by complexation. The cyclodextrins have the advantage to yield inclusion complex in solution as well as crystalline clathrates. Therefore, the absolute configuration of the guest can be obtained by determining the structure of the cyclodextrin. In this work, the first CD spectrum of 4-helicene is recorded and crystal structures of several clathrates of labile molecules are studied.     

Negative ion chemical ionization mass spectra of (η6-arene)Cr(CO)3

The negative ion chemical ionization mass spectra, with ammonia and methane as reagent gases, of the (η⁶-arene)Cr(CO)₃ complexes, where the arene is C₆H₅COCH₃, C₆H₅COC₂H₅, C₆H₅COC₃H₇, C₆H₅COC(CH₃)₃, 2-CH₃C₆H₄COC₃H₇, C₆H₅COOCH₃, C₆H₅CH₃, 1,3,5-(CH₃)₃C₆H₃ and C₆H₅CH₂COC₂H₅, are reported. Similar behaviour is observed with the two reagent gases, but ammonia shows a much higher abundance for the ions produced by reactions of [NH₂]^? with sample molecules. The compounds containing the C₆H₅CO group display an abundant [M]^{? ˙}, whereas the other compounds exhibit [M? H]^? as base peak, produced by ion/molecule reactions. A comparison of the negative ion chemical ionization mass spectra of the (η⁶-arene)Cr(CO)₃ complexes with those of the corresponding ligands shows the strong electron withdrawing power of the Cr(CO)₃ group in the gas phase.     

Formation and characterization of the hexanuclear platinum cluster [Pt6(mu-PBu(t)2)4(CO)6](CF3SO3)2 through structural, electrochemical, and computational analyses

The reaction between equimolar amounts of Pt(3)(mu-PBu(t)()(2))(3)(H)(CO)(2), Pt(3)()H, and CF(3)SO(3)H under CO atmosphere affords the triangular species [Pt(3)(mu-PBu(t)()(2))(3)(CO)(3)]X, [Pt(3)()(CO)(3)()(+)()]X (X = CF(3)SO(3)(-)), characterized by X-ray crystallography, or in an excess of acid, [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)]X(2), [Pt(6)()(2+)()]X(2)(). Structural determination shows the latter to be a rare hexanuclear cluster with a Pt(4) tetrahedral core formed by joining the unbridged sides of two orthogonal Pt(3) triangles. The dication Pt(6)()(2+)() features also extensive redox properties as it undergoes two reversible one-electron reductions to the congeners [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)](+) (Pt(6)()(+)(), E(1/2) = -0.27 V) and Pt(6)(mu-PBu(t)()(2))(4)(CO)(6) (Pt(6)(), E(1/2) = -0.54 V) and a further quasi-reversible two-electron reduction to the unstable dianion Pt(6)()(2)()(-)() (E(1/2) = -1.72 V). The stable radical (Pt(6)()(+)()) and diamagnetic (Pt(6)()) species are also formed via chemical methods by using 1 or 2 equiv of Cp(2)Co, respectively; further reduction of Pt(6)()(2+)() causes fast decomposition. The chloride derivatives [Pt(6)(mu-PBu(t)()(2))(4)(CO)(5)Cl]X, (Pt(6)()Cl(+)())X, and Pt(6)(mu-PBu(t)()(2))(4)(CO)(4)Cl(2), Pt(6)()Cl(2)(), observed as side-products in some electrochemical experiments, were prepared independently. The reaction leading to Pt(3)()(CO)(3)()(+)() has been analyzed with DFT methods, and identification of key intermediates allows outlining the reaction mechanism. Moreover, calculations for the whole series Pt(6)()(2+)() --> Pt(6)()(2)()(-)()( )()afford the otherwise unknown structures of the reduced derivatives. While the primary geometry is maintained by increasing electron population, the system undergoes progressive and concerted out-of-plane rotation of the four phosphido bridges (from D(2)(d)() to D(2) symmetry). The bonding at the central Pt(4) tetrahedron of the hexanuclear clusters (an example of 4c-2e(-) inorganic tetrahedral aromaticity in Pt(6)()(2+)()) is explained in simple MO terms.     

Complexation and Separation of Amines, Amino Acids, and Peptides by Functionalized Calix[n]arenes

The ability of calix[n]arenes to form complexes, to act as extractants in liquid–liquid extraction, and run as carriers in transport through liquid membranes of different biological amine compounds (e.g., ammonium ion, amines, amino acids, and peptides) has been the central topics of many reports. These features recommend the calix[n]arenes as competitive candidates for studying the interactions involved in host–guest recognition as well as useful receptors in separation processes. Some specific aspects of their applications in binding and separation of various amine compounds by extraction, and in transport through liquid membranes have therefore been considered. The effect of the factors that might influence the separation of above compounds by extraction, and the transport through liquid membranes using the calix [n]arenes has been presented.     

Ion-molecule reactions of gas-phase chromium oxyanions: CrxOyH z − + O2

Chromium oxyanions, Cr(x)O(y)H(z)(-), were generated in the gas-phase using a quadrupole ion trap secondary ion mass spectrometer (IT-SIMS), where they were reacted with O(2). Only CrO(2)(-) of the Cr(1)O(y)H(z)(-) envelope was observed to react with oxygen, producing primarily CrO(3)(-). The rate constant for the reaction of CrO(2)(-) with O(2) was approximately 38% of the Langevin collision constant at 310 K. CrO(3)(-), CrO(4)(-), and CrO(4)H(-) were unreactive with O(2) in the ion trap. In contrast, Cr(2)O(4)(-) was observed to react with O(2) producing CrO(3)(-) + CrO(3) via oxidative degradation at a rate that was approximately 15% efficient. The presence of background water facilitated the reaction of Cr(2)O(4)(-) + H(2)O to form Cr(2)O(5)H(2)(-); the hydrated product ion Cr(2)O(5)H(2)(-) reacted with O(2) to form Cr(2)O(6)(-) (with concurrent elimination of H(2)O) at a rate that was 6% efficient. Cr(2)O(5)(-) also reacted with O(2) to form Cr(2)O(7)(-) (4% efficient) and Cr(2)O(6)(-) + O (2% efficient); these reactions proceeded in parallel. By comparison, Cr(2)O(6)(-) was unreactive with O(2), and in fact, no further O(2) addition could be observed for any of the Cr(2)O(6)H(z)(-) anions. Generalizing, Cr(x)O(y)H(z)(-) species that have low coordinate, low oxidation state metal centers are susceptible to O(2) oxidation. However, when the metal coordination is >3, or when the formal oxidation state is > or =5, reactivity stops.     

Progress in the realisation of an autonomous environmental monitoring device for ammonia

Progress in the development of a micro-fluidic system for colorimetric monitoring of ammonia in drinking and wastewater is described. The ultimate goal is to have a miniaturised instrument that can produce accurate, reliable measurements, is easy to operate, has minimal power consumption, and can operate autonomously for a year. In this study, the indophenol reaction is incorporated into a simple, reliable analytical micro-fluidic system. Absorbance measurements for the blue ammonia-indophenol complex formed in the micro-fluidic system are shown. A key issue is the limiting stability of hypochlorite, a reagent used in the assay. The effects of hypochlorite concentration and impurities on the stability of hypochlorite are investigated and discussed. Decomposition is shown to be very dependent on the presence of heavy-metal impurities. With low levels of these catalytic metals and careful storage, hypochlorite has been shown to be stable for over a year.     

Regioselective synthesis of 4- and 5-oxazole-phosphine oxides and -phosphonates from 2H-azirines and acyl chlorides

A simple and efficient regioselective synthesis of 4-oxazole-phosphine oxides 11 and -phosphonates 12 from 2H-azirine-phosphine oxides 1 and -phosphonates 6 is described. The key step for the synthesis of oxazoles 11 is a base-mediated ring closure of vinylogous α-aminophosphorus compounds derived from phosphine oxides 4 and from phosphonates 8. These derivatives 4 and 8 are obtained by reaction of functionalized azirines 1 and 6 with acyl chlorides 2 and subsequent acid-catalyzed ring opening of N-acylaziridine-phosphine oxides 3 and -phosphonates 7. Regioselective thermal ring cleavage of N-acylaziridine-phosphine oxides 3 leads α-chloro-β-(N-acylamido)-phosphine oxides 13 and their treatment with bases gives 5-oxazole-phosphine oxides 16.     

Flavonoids in Leguminosae: analysis of extracts of T. pratense L., T. dubium L., T. repens L., and L. corniculatus L. leaves using liquid chromatography with UV, mass spectrometric and fluorescence detection

Reversed-phase LC on C-18 bonded silica with a methanol–ammonium formate gradient was used to determine the main flavonoids in leaves of four species of the Leguminosae family. The detection modes were diode-array UV absorbance, fluorescence, and (tandem) mass spectrometry. LC–UV was used for a general screening, sub-classification, and the calculation of total flavonoid contents. LC–FLU was included to identify isoflavones on the basis of their native fluorescence. Most structural information regarding aglycons, sugar moieties, and acidic groups was derived from LC–MS in both the full-scan and extracted-ion mode, using negative-ion atmospheric pressure chemical ionization. MS/MS did not provide much additional information, because the same fragments were observed as in full-scan MS.In T. pratense and T. repens, the main constituents were flavonoid glucoside–(di)malonates, while T. dubium and L. corniculatus mainly contained flavonoid (di)glycosides. Satellite sets comprising an aglycon, the glucoside and glucoside–malonates or –acetates, were abundantly present only in T. pratense. Generally speaking, the main aglycons and sugars in the four plant species are surprisingly different. In addition, while the results for T. pratense are similar to those reported in the literature, there is little agreement in the case of the other species. Finally, total flavonoid contents ranged from 50–65 mg/g for L. corniculatus and T. dubium, to 15 mg/g for T. pratense and only 1 mg/g for T. repens.     

Metal-oxygen-metal arrays in lamellar hybrid materials: cobalt and manganese 4-cyclohexene-1,2-dicarboxylates

We have obtained three layered hybrid materials from the hydrothermal reaction of 4-cyclohexene-1,2-dicarboxylic acid with Co and Mn salts: Co(C(8)H(8)O(4))[1], Mn(H(2)O)(C(8)H(8)O(4))[2], and Mn(4)(H(2)O)(C(8)H(8)O(4))(4).0.3(H(2)O)[3]. The structures for all materials were solved by single-crystal XRD ([1]P1, a=4.805(2) A, b=6.650(3) A, c=12.960(6) A, alpha=98.285(7) degrees, beta=98.986(7) degrees, gamma=95.689(7) degrees, V= 401.6(3) A(3), R(1)= 0.0438; [2] P2(1)/c, a=11.151(2) A, b=11.330(2) A, c=7.6560(15) A, beta=108.813(3) degrees , V=915.6(3) A(3), R(1)=0.0412; [3] P1, a= 11.412(3) A, b=12.136(4) A, c=13.809(4) A, alpha=104.703(6) degrees, beta=103.207(6) degrees, gamma=92.468(5) degrees, V=1790.6(9) A(3), R(1)=0.1056). While all three structures are two-dimensional overall, the metal-oxygen-metal dimensionality within the layers varies from isolated metal atoms in the case of [1] to 1D ribbons of vertex sharing MnO(6) octahedra [2] and 2D arrays of edge- and vertex-sharing polyhedra in [3].