The solid state structure of arene-mercury(II) complexes from magic-angle spinning carbon-13 NMR and the solution carbon-13 NMR of some complexes of mercury(II) with arenes having bulky aliphatic substituents

The cross-polarization magic angle spinning ¹³C NMR spectra of Hg(SbF₆)₂ - 2 Arene (Arene = C₆HMe₅, 1,2,4,5-C₆H₂Me₄, 1,2,3,4-C₆H₂Me₄, or C₆H₆) have been measured. The spectra of the complexes of C₆HMe₅ and 1,2,4,5-C₆H₂Me₄ are consistent with static η¹-bonding of the mercury to the arene at an unsubstituted carbon atom, while the spectra of the 1,2,3,4-C₆H₂Me₄ and C₆H₆ complexes show the arene to have time-averaged C_s or C₂, and C₆ symmetry respectively, at the temperature of measurement (300 K).The reduced temperature ¹³C NMR spectra of Hg(Arene)_n²⁺ (n = 1 or 2; Arene = 1,3,5-C₆H₃R₃ (R = Me, i-Pr, or t-Bu)) in SO₂ solution are also reported and affirm that in these intramolecularly mobile species the mercury bonds in an η¹-manner, with unsubstituted aryl carbon atoms being the strongly preferred point of mercury attachment. This site preference is further demonstrated by the solution ¹³C NMR spectra of Hg(Arene)_n²⁺ (Arene = 1,2,3,4-C₆H₂-Me₄, n = 1 or 2; Arene = 1,4-C₆H₄R₂, R = Me or t-Bu, n = 1). The spectra of the 1,4-C₆H₄R₂ complexes and Hg(p-C₆H₄-t-BuMe)²⁺ provide clear evidence for steric influence of the binding site.Like Hg(C₆Me₆)₂²⁺, but unlike most of the complexes of substituted benzenes which have been studied, Hg(1,3,5-C₆H₃-i-Pr₃)₂²⁺ exchanges only slowly with excess free ligand.     

Crystal structure of thiogermanic acid H(4)Ge(4)S(10)

X-ray diffraction analysis reveals the thiogermanic acid H(4)Ge(4)S(10) possesses discrete adamantane-like Ge(4)S(10)(4)(-) complex anions. Each thioanion is composed of four corner shared GeS(2.5)(-) tetrahedral units. Crystals were grown from anhydrous liquid hydrogen sulfide reactions with glassy germanium sulfide at room temperature. The crystal structure was solved and refined from single crystal diffractometer data (Mo Kalpha radiation) obtained at 173 K. H(4)Ge(4)S(10) is triclinic, centrosymmetric space group Ponemacr;, with a = 8.621(4) A, b = 9.899(4) A, c = 10.009(4) A, alpha = 85.963(7) degrees, beta = 64.714(7) degrees, gamma = 89.501(8) degrees, and Z = 2. Average bridging and terminal d(Ge-S) distances are 2.229 and 2.206 A, respectively. Vibrational mode assignments are reported from Raman scattering and IR absorption spectra of polycrystalline samples. The nu(s)(Ge-S-Ge) and nu(s)(Ge-S(-)) stretching modes are observed at 354 and 405 cm(-)(1), respectively.     

Folate antagonists. 6. Synthesis and antimalarial effects of fused 2,4-diaminothieno[2,3-d]pyrimidines

2,4-Diamino-5,7-dihydro-6H-thiopyrano[4′,3′:4,5]thieno[2,3-d]pyrirnidine, 2,4-diamino-9H-mdeno[1′,2′:4,5]thieno[2,3-d]pyrimidine, 2,4-diamino-5H-indeno[2′,1′:4,5]thieno[2,3-d]pyrimidine, 9,11-diamino-5,6-dihydronaphtho[1′,2′:4,5]thieno[2,3-d]pyrimidine, 7,9-diamino-5,6-dihydronaphtho[2′,1′:4,5]thieno[2,3-d]pyrimidine, 2,4-diamino-7-benzy]-5,6,7,8-tetrahydropyrido[4′,3′:4,5]thieno[2,3-d]pyrimidine, and various 2,4-diamino-5,6,7,8-tetrahydro-[1]benzothieno[2,3-d]pyrimidines were synthesized by cyclization of the requisite fused 2-aminothio-phenene-3-carbonitriles utilizing chloroformamidine hydrochloride in diglyme. Several compounds exhibited strong inhibitory effects against Streptococcus faecalis (MGH-2), Staphylococcus aureus (UC-76), Streptococcus faecium (ATCC 8043), Lactobacillus casei (ATCC 7469), and Pediococcus cerevisiae (ATCC 8081) in vitro, and three compounds displayed antimalarial activity against Plasmodium berghei in mice and P. falciparum (Uganda I) in vitro.     

A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O

Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.     

Coordination compounds of indium : XXXVI. The direct electrochemical synthesis of neutral and anionic organoindium halides

The electrochemical oxidation of indium metal in cells of the type leads to the formation of RInX₂ compounds; if 2,2′-bipyridine is also present, the products are the adducts RInX₂·bipy (R = CH₃, C₂H₅, C₆H₅, C₆H₅CH₂, C₆F₅; X = Cl, Br, I (not all combinations)). When R′₄NX is present instead of bipy, the products are the salts R′₄N[RInX₃]. The electrochemical oxidation apparently proceeds via the general mechanism discussed previously. Anomalous results with CH₃I or C₂H₅I are discussed in the light of the known solution chemistry of organoindium(III) compounds.     

Measurements Of Biogenic Hydrocarbons And Their Atmospheric Degradation In Forests

Abstract

An analytical procedure for the sampling and quantitative determination of biogenic hydrocarbons in the atmosphere is presented. The method is based on the adsorptive preconcentration of the hydrocarbons using Tenax TA/Carbopack B filled sampling tubes followed by thermodesorption of the trapped compounds and gas chromatographic analysis. To avoid losses of the biogenic alkenes as a consequence of their reaction with ozone on the adsorbents during the sampling step, an ozone scrubber is used in front of the adsorption tubes. Diurnal variations of the monoterpene- and ozone-concentrations are determined at different heights in and above a forest stand (coniferous and deciduous trees) in the Vosges (Col du Donon, 760 m a.s.l.) in order to elucidate the importance of terpene-oxidation reactions on the formation of peroxidic products in forest air.