Low-temperature determination of theophylline dimethyl sulfoxide solvate

The title solvate, C7H8N4O2 center dot C2H6OS, was obtained unintentionally from a cocrystal screen involving theophylline and isophthalic acid. One molecule each of theophylline and dimethyl sulfoxide is present in the asymmetric unit. The packing consists of molecular sheets lying parallel to the ( 040) series of lattice planes, in which each theophylline molecule is hydrogen bonded to one dimethyl sulfoxide molecule through an N-H center dot center dot center dot O [2.7658 (15) angstrom] hydrogen bond. This particular hydrogen-bond donor was found to be used in this type of interaction in a variety of other crystal structures of theophylline.

(Diethyleneglycol dimethyl ether)tris(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)praseodymium(III)

The title compound, [Pr(C5HF6O2)(3)(C6H14O3)] or [Pr(hfpd)(3)(2g)], was prepared by the reaction of PrCl3.7H(2)O and hfpd-H (1,1,1,5,5,5-hexafiuoropentane-2,4-dione) in the presence of aqueous ammonia and recrystallization of the product from n-hexane in the presence of diglyme (2g). The metal atom is nine-coordinate, bonded to three bidentate beta-diketonato ligands and the polyether molecule.

Marked influence of the bridging carbonyl ligands on the photo- and electrochemistry of the clusters [Ru-3(CO)(8)(mu-CO)(2)-(alpha-diimine)] (alpha-diimine = 2,2 '-bipyridine, 4,4 '-dimethyl-2,2 '-bipyridine and 2,2 '-bipyrimidine)

Bonding, photochemical and electrochemical properties of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] (alpha-diimine=2,2'-bipyridine (1), 4,4'-dimethyl-2,2'-bipyridine (2) and 2,2'-bipyrimidine (3)) are strongly influenced by the presence of bridging carbonyl ligands. Irradiation at 471 nm initially results in the population of a sigma(Ru-3)pi*(alpha-diimine) excited state. From this state, fast decay takes place to the optically hardly directly accessible pi(Ru/mu-CO) pi*(alpha-diimine) lowest excited state. These assignments agree with theoretical (TD-DFT) results, resonance Raman and picosecond time-resolved infrared spectra. The involvement of the bridging carbonyl ligands in the electron transfer increases the energetic barrier for the formation of open-structure photoproducts such as biradicals and zwitterions. Zwitterions were therefore only obtained in strongly coordinating media such as pyridine at 250 K. The bridging carbonyl ligands also stabilize the radical anions produced upon one-electron reduction of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] and observed with cyclic voltammetry, EPR and IR spectroelectrochemistry (for alpha-diimine=2,2'-bipyrimidine). In contrast, open-triangle intermediates formed along the reduction path to [Ru(CO)(2)(alpha-diimine)](n) and [Ru-2(CO)(8)](2-) are more reactive than their triosmium analogues.

A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)

A gas-phase kinetics study of the atmospherically important reaction between Cl2 and dimethyl sulfide (DMS)Cl2 + CH3SCH3 → productshas been made using a flow-tube interfaced to a photoelectron spectrometer. The rate constant for this reaction has been measured at 1.6 and 3.0 torr at T = (294 ± 2) K as (3.4 ± 0.7) × 10−14 cm3 molecule−1 s−1. Reaction (1) has been found to proceed via an intermediate, (CH3)2SCl2, to give CH3SCH2Cl and HCl as the products. The mechanism of this reaction and the structure of the intermediate were investigated using electronic structure calculations. A comparison of the mechanisms of the reactions between Cl atoms and DMS, and Cl2 and DMS has been made and the relevance of the results to atmospheric chemistry is discussed.

Conformational studies of mixed-ligand copper(II) chelates. Crystal and molecular structure of (N,N-dimethyl-N′-ethyl-1,2-diaminoethane-(1-phenyl-1,3,-butanedionato)copper(II) perchlorate

The IR and ligand field spectra and the structure of the mixed-ligand compound [N,N-dimethyl-N′-ethyl-1,2-diaminoethane(1-phenyl-1,3-butanedionato)(perchlorato)copper(II)]), [Cu(dmeen)bzac(OClO3)], are reported. The structure was determined by single crystal X-ray diffraction analysis (triclinic, space group ). The structure is square pyramidal with the apical position occupied by one oxygen of the tetrahedral perchlorato group (distance from copper 2.452(5) Å). The plane of the phenyl ring is tilted forming an angle of 16.72(14)° with the plane of the β-dionato moiety. The nitrogenous base adopts the gauche conformation with torsional angle of 108.72(14)°. The ethyl group is cis oriented relative to the phenyl group, occupying the equatorial position with the vector of the carbon-nitrogen bond forming an angle of 143.9(3)° with the CuNN plane. The interactions of the adjacent axial hydrogen with an oxygen of the perchlorato group result in hydrogen bond formation. The IR spectra reveal that in the solid state the Br− or Cl− displace easily the ClO4− group. The shifts in the ligand field spectra indicate that polar solvents participate in donor-acceptor interactions with the metal centre along an axis perpendicular to the CuN2O2 plane.

Synthesis and X-ray crystal and molecular structure of tetrakis(2,2-dimethyl-1-phenylethenyl)chromium(IV), the first structurally-characterised homoleptic alkenyl compound of a transition metal

The title compound, the first homoleptic Group 6A metal alkenyl, has been prepared from CrCl3·3(thf), and its properties, including X-ray crystal structure determination, are reported.

Monitoring the penetration enhancer dimethyl sulfoxide in human stratum corneum in vivo by confocal raman spectroscopy

The stratum corneum (SC) barrier typically consists of layers of corneocytes embedded in a lipid continuum that regulates barrier function. The lipid domain containing ceramides, cholesterol, and free fatty acids provides the major pathway for most drugs permeating across SC. Penetration enhancers diminish the SC barrier function. The classic enhancer is dimethyl sulfoxide (DMSO). Its mechanisms of action remain unclear, although DMSO disrupts lipid organisation and may displace protein-bound water. Here we use confocal Raman spectroscopy to probe molecular interactions between a finite (depleting) dose of DMSO and SC, as functions of depth and time, providing novel information about residence time and location of DMSO in human SC in vivo

Synthesis, chemical, electrochemical characterization of oxomolybdenum(V) complexes of 2-(3,5-dimethyl pyrazol-1-yl) benzothiazole ligand: crystal structure of ligand and oxomolybdenum(VI) complex and density functional theory (DFT) calculation

This work reports the ligational behavior of the neutral bidentate chelating molecule 2-(3,5-dimethyl pyrazol-1-yl) benzothiazole towards the oxomolybdenum(V) center. Both mononuclear complexes of the type (MoOX3L)-O-V and binuclear complexes of the formula (Mo2O4X2L2)-O-V (where X = Cl, Br) are isolated in the solid state. The complexes are characterized by elemental analyses, various spectroscopic techniques (UV-Vis IR), magnetic susceptibility measurement at room temperature, and cyclic voltammetry for their redox behavior at a platinum electrode in CH3CN. The mononuclear complexes (MoOX3L)-O-V are found to be paramagnetic while the binuclear complexes Mo2O4X2L2 are diamagnetic. Crystal and molecular structure of the ligand and the dioxomolybdenum complex (MoO2Br2L)-O-VI (obtained from the complex MoOBr3L during crystallization) have been solved by single crystal X-ray diffraction technique. Relevant DFT calculations of the ligand and the complex (MoO2Br2L)-O-VI are also carried out.

Internal rotation in dimethylacetylene

The vibrational spectrum of dimethyl acetylene has been remeasured with better resolving power than hitherto, and the rotational fine structure of some perpendicular type bands has been partly analyzed. The energy levels of a molecule of this kind in which internal rotation of methyl groups may arise have been re-examined theoretically and the rotational structure of the absorption bands has been more clearly defined than previously. The experimental results are consistent with the assumption of unrestricted internal rotation of the methyl groups, and the Coriolis factors $\zeta _{i}$ for several vibrations have been determined.

Intensities in infrared bands V: Bond polar properties in dimethylacetylene

The absolute intensities of all except one of the infra-red fundamental vibration bands of dimethyl acetylene have been determined, and the results have been used to compute polar properties of the C—H and C—C bonds. It has been found that if the very probable assumption is made that the acetylenic carbon atoms carry a residual negative charge, the hydrogen atoms in the C—H bonds must carry a residual positive charge. The probable value of the C—H dipole is about 04 Debye, and that of the C—C bond about 1 Debye. Comparisons have been made with the results of similar work with related molecules.

Molybdenum eta(3)-allyl dicarbonyl complexes as a new class of precursors for highly reactive epoxidation catalysts with tert-butyl hydroperoxide

New Mo(II) diimine derivatives of [Mo(q (3)allyl)X(CO)(2)(CH3CN)(2)] (allyl = C3H5 and C5H5O; X = Cl, Br) were prepared, and [MO(eta(3)-C3H5)Cl(CO)(2)(BIAN)] (BIAN = 1,4-(4-chloro)phenyl-2,3-naphthalene-diazabutadiene) (7) was structurally characterized by single-crystal X-ray diffraction. This complex adopted an equatorial-axial arrangement of the bidentate ligand (axial isomer), in contrast with the precursors, found as the equatorial isomer in the solid and fluxional in solution. The new complexes of the type [Mo(eta(3)-allyl)X(CO)(2)(N-N)l (N-N is a bidentate chelating dinitrogen ligand) were tested for the catalytic epoxidation of cyclooctene using tert-butyl hydroperoxide as oxidant. All catalytic systems were 100% selective toward epoxide formation. While their turnover frequencies paralleled those of related Mo(eta) carbonyl compounds or Mo(VI) compounds bearing similar N-donor ligands, they exhibited similar olefin conversions in consecutive catalytic runs. The acetonitrile precursors were generally more active than the diimine complexes, and the chloro derivatives more active than the bromo ones. Combined vibrational and NMR spectroscopy and computational studies (DFT) were used to investigate the nature of the molybdenum species formed in the catalytic system with [Mo(eta(3)-C3H5)Cl(CO)(2){1,4-(2,6-dimethyl)phenyl-2.3-dimethyldiazabuta diene}] (4) and to propose that the resulting species may be dimeric bearing oxide bridges.

Direct time-resolved study of the gas-phase reactions of germylene with ethyl- and diethylgermane: absolute rate constants, temperature dependences, and mechanism

Time-resolved studies of germylene, GeH2, generated by the 193 nm laser flash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reactions with ethyl- and diethylgermanes in the gas phase. The reactions were studied over the pressure range 1-100 Torr with SF6 as bath gas and at five temperatures in the range 297-564 K. Only slight pressure dependences were found for GeH2 + EtGeH3 (399, 486, and 564 K). The high pressure rate constants gave the following Arrhenius parameters: for GeH2 + EtGeH3, log A = -10.75 +/- 0.08 and E-a = -6.7 +/- 0.6 kJ mol(-1); for GeH2 + Et2GeH2, log A = -10.68 +/- 0.11 and E-a = -6.95 +/- 0.80 kJ mol(-1). These are consistent with fast, near collision-controlled, association processes at 298 K. RRKM modeling calculations are, for the most part, consistent with the observed pressure dependence of GeH2 + EtGeH3. The ethyl substituent effects have been extracted from these results and are much larger than the analogous methyl substituent effects in the SiH2 + methylsilane reaction series. This is consistent with a mechanistic model for Ge-H insertion in which the intermediate complex has a sizable secondary barrier to rearrangement.

Gas phase kinetic and quantum chemical studies of the reactions of silylene with the methylsilanes. Absolute rate constants, temperature dependences, RRKM modelling and potential energy surfaces

Time resolved studies of silylene, SiH2, generated by the 193 nm laser. ash photolysis of phenylsilane, have been carried out to obtain rate coefficients for its bimolecular reactions with methyl-, dimethyl- and trimethyl-silanes in the gas phase. The reactions were studied over the pressure range 3 - 100 Torr with SF6 as bath gas and at five temperatures in the range 300 - 625 K. Only slight pressure dependences were found for SiH2 + MeSiH3 ( 485 and 602 K) and for SiH2 + Me2SiH2 ( 600 K). The high pressure rate constants gave the following Arrhenius parameters: [GRAPHICS] These are consistent with fast, near to collision-controlled, association processes. RRKM modelling calculations are consistent with the observed pressure dependences ( and also the lack of them for SiH2 + Me3SiH). Ab initio calculations at both second order perturbation theory (MP2) and coupled cluster (CCSD(T)) levels, showed the presence of weakly-bound complexes along the reaction pathways. In the case of SiH2 + MeSiH3 two complexes, with different geometries, were obtained consistent with earlier studies of SiH2 + SiH4. These complexes were stabilised by methyl substitution in the substrate silane, but all had exceedingly low barriers to rearrangement to product disilanes. Although methyl groups in the substrate silane enhance the intrinsic SiH2 insertion rates, it is doubtful whether the intermediate complexes have a significant effect on the kinetics. A further calculation on the reaction MeSiH + SiH4 shows that the methyl substitution in the silylene should have a much more significant kinetic effect ( as observed in other studies).