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21.
From a range of preparative methods, three geometric isomers of bis(diphenylarsino)methane‐dichloroplatinum(II) have been isolated, viz. cis‐PtCl2(dpam), trans, trans‐Pt2Cl4(dpam)2 and cis, trans‐Pt2Cl4(dpam)2. Their structures were determined by single‐crystal X‐ray diffraction. 相似文献
22.
Deacon GB Delbridge EE Evans DJ Harika R Junk PC Skelton BW White AH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(5):1193-1204
Sodium and potassium tetrakis(3,5-di-tert-butylpyrazolato)lanthanoidate(III) complexes [M[Ln(tBu(2)pz)(4)]] have been prepared by reaction of anhydrous lanthanoid trihalides with alkali metal 3,5-di-tert-butylpyrazolates at 200-300 degrees C, and a 1,2,4,5-tetramethylbenzene flux for M=K. On extraction with toluene (or occasionally directly from the reaction tube) the following complexes were isolated: [Na(PhMe)[Ln(tBu(2)pz)(4)]] (1 Ln; 1 Ln=1 Tb, 1 Ho, 1 Er, 1 Yb), [K(PhMe)[Ln(tBu(2)pz)(4)]].2 PhMe (2 Ln; 2 Ln=2 La, 2 Sm, 2 Tb, 2 Ho, 2 Yb, 2 Lu), [Na[Ln(tBu(2)pz)(4)]](n) (3 Ln; 3 Ln=3 La, 3 Tb, 3 Ho, 3 Er, 3 Yb), [K[Ln(tBu(2)pz)(4)]](n) (4 Ln; 4 Ln=4 La, 4 Nd, 4 Sm, 4 Tb, 4 Ho, 4 Er, 4 Yb, 4 Lu), with the last two classes generally being obtained by loss of toluene from 1 Ln or 2 Ln, and [Na(tBu(2)pzH)[Ln(tBu(2)pz)(4)]].PhMe (5 Ln; 5 Ln=5 Nd, 5 Er, 5 Yb). Extraction with 1,2-dimethoxyethane (DME) after isolation of 2 Ho yielded [K(dme)[Ho(tBu(2)pz)(4)]] (6 Ho). X-ray crystal structures of 1 Ln (=1 Tb, 1 Ho; P2(1)/c), 2 Ln (=2 La, 2 Sm, 2 Tb, 2 Yb, 2 Lu; Pnma), 3,4 Ln (=3 La, 3 Er, 4 Sm; P2(1)/m), and 5 Ln (=5 Nd, 5 Er, and 5 Yb; P1) show each group to be isomorphous regardless of the size of the Ln(3+) ion. All complexes contain eight-coordinate [Ln(eta(2)-tBu(2)pz)(4)] units. These are further linked to the alkali metal by bridging through two (1,2,5 Ln) or three (3,4 Ln) tBu(2)pz groups which show striking coordination versatility. Sodium is coordinated by an eta(4)-PhMe, a micro-eta(2):eta(2)-tBu(2)pz, and a micro-eta(4)(Na):eta(2)(Ln)-tBu(2)pz ligand in 1 Ln, and by one eta(1)-tBu(2)pzH and two micro-eta(3)(Na):eta(2)(Ln) ligands in 5 Ln. By contrast, potassium has one eta(6)-PhMe and two micro-eta(5)(K):eta(2)(Ln) ligands in 2 Ln. Classes 3,4 Ln form polymeric chains with the alkali metal bonded by two micro-eta(3)(NNC-M):eta(2)(Ln)-tBu(2)pz ligands within [MLn(tBu(2)pz)(4)] units which are joined together by eta(1)(C)-tBu(2)pz-Na, K linkages. 相似文献
23.
Abbott AP Capper G Davies DL Rasheed RK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3769-3774
A dark green, viscous liquid can be formed by mixing choline chloride with chromium(III) chloride hexahydrate and the physical properties are characteristic of an ionic liquid. The eutectic composition is found to be 1:2 choline chloride/chromium chloride. The viscosity and conductivity are measured as a function of temperature and composition and explained in terms of the ion size and liquid void volume. The electrochemical response of the ionic liquid is also characterised and it is shown that chromium can be electrodeposited efficiently to yield a crack-free deposit. This approach could circumvent the use of chromic acid for chromium electroplating, which would be a major environmental benefit. This method of using hydrated metal salts to form ionic liquids is shown to be valid for a variety of other salt mixtures with choline chloride. 相似文献
24.
Hitzbleck J O'Brien AY Forsyth CM Deacon GB Ruhlandt-Senge K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(13):3315-3323
Two series of heavy alkaline earth metal pyrazolates, [M(Ph(2)pz)(2)(thf)(4)] 1 a-c (Ph(2)pz=3,5-diphenylpyrazolate, M=Ca, Sr, Ba; THF=tetrahydrofuran) and [M(Ph(2)pz)(2)(dme)(n)] (M=Ca, 2 a, Sr, 2 b, n=2; M=Ba, 2 c, n=3; DME=1,2-dimethoxyethane) have been prepared by redox transmetallation/ligand exchange utilizing Hg(C(6)F(5))(2). Compounds 1 a and 2 b were also obtained by redox transmetallation with Tl(Ph(2)pz). Alternatively, direct reaction of the alkaline earth metals with 3,5-diphenylpyrazole at elevated temperatures under solventless conditions yielded compounds 1 a-c and 2 a-c upon extraction with THF or DME. By contrast, [M(Me(2)pz)(2)(Me(2)pzH)(4)] 3 a-c (M=Ca, Sr, Ba; Me(2)pzH=3,5-dimethylpyrazole) were prepared by protolysis of [M[N(SiMe(3))(2)](2)(thf)(2)] (M=Ca, Sr, Ba) with Me(2)pzH in THF and by direct metallation with Me(2)pzH in liquid NH(3)/THF. Compounds 1 a-c and 2 a-c display eta(2)-bonded pyrazolate ligands, while 3 a,b exhibit eta(1)-coordination. Complexes 1 a-c have transoid Ph(2)pz ligands and an overall coordination number of eight with a switch from mutually coplanar Ph(2)pz ligands in 1 a,b to perpendicular in 1 c. In eight coordinate 2 a,b the pyrazolate ligands are cisoid, whilst 2 c has an additional DME ligand and a metal coordination number of ten. By contrast, 3 a,b have octahedral geometry with four eta(1)-Me(2)pzH donors, which are hydrogen-bonded to the uncoordinated nitrogen atoms of the two trans Me(2)pz ligands. The application of synthetic routes initially developed for the preparation of lanthanoid pyrazolates provides detailed insight into the similarities and differences between the two groups of metals and structures of their complexes. 相似文献
25.
Surface enhanced Raman spectroscopy (SERS) is a rapid and highly sensitive spectroscopic technique that has the potential to measure chemical changes in bacterial cell surface in response to environmental changes. The objective of this study was to determine whether SERS had sufficient resolution to differentiate closely related bacteria within a genus grown on solid and liquid medium, and a single Arthrobacter strain grown in multiple chromate concentrations. Fourteen closely related Arthrobacter strains, based on their 16S rRNA gene sequences, were used in this study. After performing principal component analysis in conjunction with Linear Discriminant Analysis, we used a novel, adapted cross-validation method, which more faithfully models the classification of spectra. All fourteen strains could be classified with up to 97% accuracy. The hierarchical trees comparing SERS spectra from the liquid and solid media datasets were different. Additionally, hierarchical trees created from the Raman data were different from those obtained using 16S rRNA gene sequences (a phylogenetic measure). A single bacterial strain grown on solid media culture with three different chromate levels also showed significant spectral distinction at discrete points identified by the new Elastic Net regularized regression method demonstrating the ability of SERS to detect environmentally induced changes in cell surface composition. This study demonstrates that SERS is effective in distinguishing between a large number of very closely related Arthrobacter strains and could be a valuable tool for rapid monitoring and characterization of phenotypic variations in a single population in response to environmental conditions. 相似文献
26.
AS Chesman DR Turner B Moubaraki KS Murray GB Deacon SR Batten 《Dalton transactions (Cambridge, England : 2003)》2012,41(36):10903-10909
The synthesis of two high nuclearity lanthanoid clusters demonstrates the versatility of the carbonate anion as a robust cluster forming agent, potentially allowing for the formation of otherwise inaccessible core topologies. The complexes, [Gd(14)(CO(3))(13)(ccnm)(9)(OH)(H(2)O)(6)(phen)(13)(NO(3))](CO(3))(2.5)·(phen)(0.5) () and [Dy(14)(CO(3))(13)(ccnm)(10)(OH)(H(2)O)(6)(phen)(13)](CO(3))(2.5)·(phen)(0.5) () (ccnm = carbamoylcyanonitrosomethanide, phen = 1,10-phenanthroline), contain a [Ln(14)(CO(3))(13)(OH)] core in which the carbonate anions display four unique coordination modes. The complexes are chiral, and the ccnm ligands also display four unique coordination modes. Extensive intra- and intermolecular π-π stacking between phen ligands leads to the formation of 1D chains in the crystal structure. Both complexes display magnetic properties that are indicative of antiferromagnetic coupling, with complex displaying behaviour consistent with possible single molecule magnet properties. 相似文献
27.
Kopreski RP Briggs JB Lin W Jazdzyk M Miller GP 《The Journal of organic chemistry》2012,77(3):1308-1315
Several o-quinodimethane adducts of [60]fullerene were synthesized and their intramolecular aryl CH-fullerene π interactions were studied using variable temperature-NMR (VT-NMR). Evaluation of the rate constants associated with the first-order transition states for cyclohexene boat-to-boat inversions enables quantification of ΔG(?) values for each inversion. A comparison between two constitutional isomers, only one of which is capable of intramolecular CH-π interactions, provides a lower limit of 0.95 kcal/mol for each aryl CH-fullerene π interaction. 相似文献
28.
Summary A genetic algorithm has been designed which generates molecular structures within constraints. The constraints may be any useful function, for example an enzyme active site, a pharmacophore or molecular properties from pattern recognition or rule-induction analyses. The starting point may be random or may utilise known molecules. These are modified to grow into families of structures which, using the evolutionary operators of selection, crossover and mutation evolve to better fit the constraints. The basis of the algorithm is described together with some applications in lead generation, 3D database construction and drug design. Genetic algorithms of this type may have wider applications in chemistry, for example in the design and optimisation of new polymers, materials (e.g. superconducting materials) or synthetic enzymes. 相似文献
29.
Glen B. Deacon Ewan E. Delbridge Brian W. Skelton Allan H. White 《Angewandte Chemie (International ed. in English)》1998,37(16):2251-2252
A higher degree of coordination saturation is attainable through the unusual coordination mode in the title compound 1 , in which the central pyrazolate groups function both as chelating and as bridging ligands. There is some asymmetry in the bridging, and the N atoms of each μ-η2:η2-pyrazolato ligand are 0.07–0.11 Å closer to one of the two Yb centers. 相似文献
30.
Thomas Behrsing Glen B. Deacon Peter C. Junk Brian W. Skelton Alexandre N. Sobolev Allan H. White 《无机化学与普通化学杂志》2013,639(1):41-48
Reaction of LnCl3 with Na2(PDDA) (PDDA = phenylene‐1, 2‐dioxydiacetate) in a 1 to 2 mol ratio in aqueous solution yielded [Ln2(PDDA)3(H2O)6] · 2H2O, structurally characterized for Ln = Ce ( 1 ), Sm ( 2 ) (redetermination), Tb ( 3 ) and Y ( 4 ) in a monoclinic C2/c array, a second related structural form [orthorhombic, Pbcn] being obtained for Tb ( 5 ), Ho ( 6 ) and Er ( 7 ). The ‘domains of existence' of these two previously described forms are now extended to Ce–Dy, Y, and Eu–Er, respectively. Reaction under the same conditions for the heavier Yb3+ ion yielded [Yb2(PDDA)3(H2O)6](∞|∞) · 4H2O ( 8 ), orthorhombic, Pbca. In the case of Ln = La the bimetallic species [NaLa(PDDA)2(H2O)2](∞|∞) · 4H2O ( 9 ) was obtained, while reaction of LnCl3 with Na2(PDDA) in a 1 to 3 mol ratio led to the isolation of the isotypic (monoclinic, P21/c) [NaLn(PDDA)2(H2O)2](∞|∞) · 4H2O) for Ln = Ce ( 10 ) and Sm ( 12 ). With the smaller Ln = Yb, the more definitively bimetallic [NaYb(PDDA)2(H2O)2](∞|∞) · 3H2O ( 13 ) (triclinic, P$\bar{1}$ )) was obtained, the trihydrate solvation ascribed differing from that recorded (dihydrate) in a cosynchronous report. 相似文献