5,6-Di-methyl-benzo[d][1,3]oxatellurole.

The structure of the title compound, C9H10OTe, at 100 K has ortho-rhom-bic (P21212) symmetry with two independent mol-ecules in the asymmetric unit (Z' = 2). The mol-ecules are folded along their Te⋯O axes, with their Te-C-O planes angled at an average of 25.1° with respect to the remaining non-H atoms, which are almost coplanar (average deviation from planarity = 0.04 Å). A Hirshfeld plot shows weak inter-molecular inter-actions between the two Te atoms located in each asymmetric mol-ecule, with a Te⋯Te distance of 3.7191 (4) Å. The structure is strongly pseudosymmetric to the space group Pccn with Z' = 1. The crystal chosen for data collection was found to be was an inversion twin.

[1,4]Ditellurino[2,3-b:5,6-b']di-pyrazine.

[1,4]Ditellurino[2,3-b:5,6-b']di-pyrazine represents the first reported [1,4]chalcogena[2,3-b:5,6-b']di-pyrazine containing a heavy chalcogens The asymmetric unit consists of three mol-ecules. In contrast to its sulfur analog, which is planar [Lynch et al. (1994 ▸) Cryst. Struct. Commun. 50,1470-1472], C8H4N4Te2 is folded along the Te⋯Te axis to accommodate the larger chalcogenide atoms. The dihedral angle between the two Te2C2 rings of the central ring is 57.9° (mean of three). C-Te bond lengths range from 2.1105 (16) Što 2.1381 (17) Å, in good agreement with those predicted by their covalent radii. All Te atoms are involved in inter-molecular Te⋯N contacts, with distances in the range 2.894 (2) to 2.963 (2) Å. These result in a spiral supra-molecular assembly, forming helical columns.

Hydrogen-Deuterium Exchange in Basic Near-Critical and Supercritical Media: An Experimental and Theoretical Study.

Treatment of homo- and heterocyclic aromatic substrates with basic deuterium oxide under near- or supercritical conditions results in rapid base-catalyzed hydrogen-deuterium exchange (HDE) in aromatic and benzylic positions. It has been postulated that HDE follows a simple deprotonation-reprotonation mechanism, but little evidence has been provided to date. This study correlates experimentally observed proton exchanges in n-butylbenzene with ab initio calculations of the acidities and potential energy (PE) profiles. In addition to providing further support for carbanion intermediacy in HDE, these results offer new insights into substrate acidities in near- and supercritical aqueous media and the optimal conditions required for their isotope exchange.

Dinuclear metal(ii)-acetato complexes based on bicompartmental 4-chlorophenolate: syntheses, structures, magnetic properties, DNA interactions and phosphodiester hydrolysis.

A series of dinuclear metal(ii)-acetato complexes: [Ni2(µ-L(Cl)O)(µ2-OAc)2](PF6)·3H2O (1), [Ni2(µ-L(Cl)O)(µ2-OAc)2](ClO4)·CH3COCH3 (2), [Cu2(µ-L(Cl)O)(µ2-OAc)(ClO4)](ClO4) (3), [Cu2(µ-L(Cl)O)(OAc)2](PF6)·H2O (4), [Zn2(µ-L(Cl)O)(µ2-OAc)2](PF6) (5) and [Mn2(L(Cl)-O)(µ2-OAc)2](ClO4)·H2O (6), where L(Cl)O(-) = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenolate, were synthesized. The complexes were structurally characterized by spectroscopic techniques and single crystal X-ray crystallography. Six-coordinate geometries with doubly bridged acetato ligands were found in Ni(ii), Zn(ii) and Mn(ii) complexes 1, 2, 5 and 6, whereas with Cu(ii) complexes a five-coordinate species was obtained with 4, and mixed five- and six-coordinate geometries with a doubly bridged dimetal core were observed in 3. The magnetic properties of complexes 1-4 and 6 were studied at variable temperatures and revealed weak to very weak antiferromagnetic interactions in 1, 2, 4 and 6 (J = -0.55 to -9.4 cm(-1)) and ferromagnetic coupling in 3 (J = 15.4 cm(-1)). These results are consistent with DFT calculations performed at the B3LYP/def2-TZVP(-f) level of theory. Under physiological conditions, the interaction of the dinculear complexes 1-5 with supercoiled plasmid ds-DNA did not show any pronounced nuclease activity, but Ni(ii) complexes 1 and 2 revealed a strong ability to unwind the supercoiled conformation of ds-DNA. The mechanistic studies performed on the interaction of the Ni(ii) complexes with DNA demonstrated the important impact of the nickel(ii) ion in the unwinding process. In combination with the DNA study, the phosphatase activity of complexes 1, 3, and 5 was examined by the phosphodiester hydrolysis of bis(2,4-dinitrophenol)phosphate (BDNPP) in the pH range of 5.5-10.5 at 25 °C. The Michaelis-Menten kinetics performed at pH 7 and 10.7 showed that catalytic efficiencies kcat/KM (kcat = catalytic rate constant, KM = substrate binding constant) decrease in the order: Ni(ii), 1 > Zn(ii), 5 > Cu(ii), 3. A similar trend was also observed with the turnover numbers at pH = 7. The results are discussed in relation to the coordination geometry and nature of the metal center as well as the steric environment imposed by the compartmental phenoxido ligand.

The first crystal structures of six- and seven-membered tellurium- and nitrogen-containing (Te-N) heterocycles: 2H-1,4-benzotellurazin-3(4H)-one and 2,3-dihydro-1,5-benzotellurazepin-4(5H)-one.

There is a paucity of data concerning the structures of six- and seven-membered tellurium- and nitrogen-containing (Te-N) heterocycles. The title compounds, C8H7NOTe, (I), and C9H9NOTe, (II), represent the first structurally characterized members of their respective classes. Both crystallize with two independent molecules in the asymmetric unit. When compared to their sulfur analogs, they exhibit slightly greater deviations from planarity to accommodate the larger chalcogenide atom, with (II) adopting a pronounced twist-boat conformation. The C-Te-C angles of 85.49 (15) and 85.89 (15)° for the two independent molecules of (I) were found to be somewhat smaller than those of 97.4 (2) and 97.77 (19)° for the two independent molecules of (II). The C-Te bond lengths [2.109 (4)-2.158 (5) Å] are in good agreement with those predicted by the covalent radii. Intermolecular N-H...O hydrogen bonding in (I) forms centrosymmetric R2(2)(8) dimers, while that in (II) forms chains. In addition, intermolecular Te...O contacts [3.159 (3)-3.200 (3) Å] exist in (I).

Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.

The reaction of a methanolic solution containing the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (L(Cl)-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(ii) complexes [Co2(µ-L(Cl)O)(H2O)2Cl2][Co2(µ-L(Cl)O)(MeOH)2Cl2](PF6)2 (), [Ni2(µ-L(Cl)O)(MeOH)2Cl2]PF6 (), [Ni2(µ-L(Cl)O)(MeOH)(H2O)Cl2]ClO4·1.25H2O (), [Cu2(µ-L(Cl)O)Cl2]PF6·1/2MeOH () and [Zn2(µ-L(Cl)O)Cl2]PF6·MeOH (). The complexes were characterized by elemental microanalyses, conductivity measurements, IR and UV-Vis spectroscopy, mass spectrometry and single crystal X-ray crystallography. Each M(ii) center within the dinuclear complex cations is octahedrally coordinated in complexes , and five-coordinated distorted square pyramidal in and . Magnetic susceptibility measurements at variable temperature of the complexes revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm(-1), respectively. The results of DFT calculations correlate well with the experimentally determined antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, MM distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed.

Preparation of deuterium-labeled biotransformation products of 2,4,6-trinitrotoluene.

Methods for the preparation of deuterium-labeled analogs to six prominent biotransformation products of the explosive 2,4,6-trinitrotoluene were developed. These are useful as reference standards for stable isotope dilution techniques and for solid state (2)H NMR spectroscopic studies. Although syntheses for most of the target compounds in protiated form had been reported in the past, most of those were found to be poorly suited for the preparation of the deuterated materials. Selective reduction of [(2)H5]trinitrotoluene furnished [(2)H5]-4,6-dinitro-2-hydroxylaminotoluene, [(2)H5]-2,6-dinitro-4-hydroxylaminotoluene, [(2)H5]-2-amino-4,6-dinitrotoluene, and [(2)H5]-4-amino-2,6-dinitrotoluene. The syntheses of [(2)H10]-2,2'-azo-4,4',6,6'-tetranitrotoluene and [(2)H10]-4,4'-azo-2,2',6,6'-tetranitrotoluene were accomplished by selective oxidation of [(2)H5]-2-amino-4,6-dinitrotoluene and [(2)H5]-4-amino-2,6-dinitrotoluene, respectively.

1-Chlorofuro[3,2-e][2,1,3]benzoxatellurazole.

The title compound, C(8)H(4)ClNO(2)Te, represents the first reported example of a benzofuran-derived 2,1,3-benzoxatellurazole derivative. While it can be formally described as a nitrosoaryltellurium monochloride, its Te-O and Te-C bond lengths of 2.1421 (14) and 2.0374 (17) Å, respectively, characterize it as a planar tricyclic aromatic containing a Te=C double bond. Its formation suggests that derivatives of 2-cyclohexenone oxime in general react with tellurium dioxide to form aryl-2,1,3-benzoxatellurazoles.

Effects of static vs. tidal hydrology on pollutant transformation in wetland sediments.

This work addressed effects of hydrology on biogeochemical processes relevant to pollutant chemical transformation in wetland sediments. Microcosms were designed to impose three hydrologic conditions on salt marsh sediments: (i) drained-oxidized redox potenial (Eh); (ii) flooded-reduced Eh and, (iii) diurnal tide-oscillating Eh. The test chemicals were N- and/or S-heterocycles (NSHs) including quinoxaline (1,4-benzodiazine), 2-methylquinoxaline(2-methyl-1,4-benzodiazine), 2,3-dimethylquinoxalinen (2,3-dimethyl-1,4-benzodiazine), phenazine (2,3,5,6-dibenzo-1,4-diazine), acridine (2,3,5,6-dibenzopyridine), dibenzothiophene (2,3,5-dibenzothiophene), phenothiazine (dibenzo-1,4-thiazine), and phenanthridine (2,3-benzoisoquinoline). Biogeochemical processes reflected the hydrologic conditions in ways analogous to field settings, e.g., Eh characteristics were drastically different: static (flooded and drained) systems had reduced (mu = -428 mV +/- 57) and oxidized (mu = +73 mV +/- 32) values, respectively, with no evidence of periodic variation while the tidal systems exhibited regularly oscillating Eh (amplitudes 40-250 mV). Sediment trace gases also corresponded to the Eh, with the major species detected being CO2 and H2O (drained, tidal) vs. CO2 + H2O + sulfides + methane (flooded). The NSH transformation rates were different in each hydrologic regime and decreased as follows: tidal > or = drained >> flooded. These results indicated that there were subtle differences in NSH processing in drained and tidal systems, but both of these systems transformed NSHs faster and to lower levels than flooded sediments. These data suggest that in situ remediation options that preserve wetland integrity and tidal hydrology can be as or more effective than static conditions that obtain in approaches such as impoundment and excavation-upland placement.

Tribromo(3,5-dimethyl-2-nitrophenyl-kappa(2)C(1),O)tellurium(IV), bromo(3,5-dimethyl-2-nitrophenyl-kappa(2)C(1),O)tellurium(II) and bromo(3,5-dimethyl-2-nitrosophenyl-kappa(2)C(1),O)tellurium(II).

All three title compounds, prepared from bis(3,5-dimethyl-2-nitrophenyl)ditellurium, exhibit high degrees of intramolecular Te-O coordination. Their Te-O distances increase in the order C(8)H(8)BrNOTe < C(8)H(8)BrNO(2)Te < C(8)H(8)Br(3)NO(2)Te, with distances of 2.165 (3), 2.306 (1) and 2.423 (6) A, respectively, indicating that C(8)H(8)BrNOTe may be more aptly described as 1-bromo-4,6-dimethyl-2,1,3-benzoxatellurazole.

Sonochemical degradation of aromatic organic pollutants.

This work examines the use of ultrasound to mineralize 4-chlorophenol, 2,4-dichlorophenol, [aryl-2H3]2,4-dichlorophenol, 4-chloro-3,5-dimethylphenol, 4-fluorophenol, 2,4,6-trinitrotoluene, 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene in dilute aqueous solution. Mineralization rates were determined as a function of substrate structure and concentration, bulk phase temperature, pH and the presence of co-solutes such as detergents and humic acids. All substrates were found to degrade sonochemically, as evidenced by the release of Cl- and NO3- respectively. Product analyses by GC-MS, HPLC, and micellar electrokinetic capillary chromatography (MECC) indicated mineralization with little formation of organic byproducts, a significant advantage over other remediation methods. Chloride release from chlorophenols was approximately proportional to substrate total chlorine content, irrespective of structural differences, and reached 80% of the theoretical limit. Fluoride release from 4-fluorophenol was ca. 10-fold lower than that of chloride from 4-chlorophenol. Changes in the bulk phase temperature from 9.5 to 34 degrees C, and 12.5 to 30 degrees C, respectively, were of little consequence to observed mineralization rates for nitroaromatics and chlorophenols. A significant mineralization rate increase resulted from sonication of 4-chlorophenol in acidified media. Additions of amphiphilic co-solutes resulted in modest, but statistically significant, sonolysis enhancements.