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81.
Crystalline [Li{N(SiMe2OMe)C(tBu)C(H)(SiMe3)}]2 (5), [Li{N(SiMe2OMe)C(Ph)C(H)(SiMe3)}]2 (6), [C(C6H3Me2-2,5)C(H)(SiMe3)}(TMEDA)](7), [Li{N(SiMe(OMe)2)C(tBu)C(H)(SiMe3)}(THF)]2 (8), Li{N(SiMe(OMe)2)C(Ph)C(H)(SiMe3)}(TMEDA) (9) and [Li{N(SiMe2OMe)C(tBu)C(H)(SiMe2OMe)}]2 (10) were readily obtained at ambient temperature from (i) [Li{CH(SiMe3)(SiMe2OMe)}]8 (1) and an equivalent portion of RCN (R=tBu (5), Ph (6) or 2,5-Me2C6H3 (7)); (ii) [Li{CH(SiMe3)(SiMe(OMe)2)}]∞ (2) and an equivalent portion of tBuCN (8) or PhCN (9); and (iii) [Li{CH(SiMe2OMe)2}]∞ (3) and one equivalent of tBuCN (10). Reactions (i) and (ii) were regiospecific with SiMe3−n(OMe)n>SiMe3 in 1,3-migration from C (in 1 or 2)→N. The 1-azaallyl ligand was bound to the lithium atom as a terminally bound κ1-enamide (8 and 10), a bridging η3-1-azaallyl (6), or a bridging κ1-enamide (5). The stereochemistry about the CC bond was Z for 5, 8 and 10 and E for 7. X-ray data are provided for 5, 6, 7, 8 and 10 and multinuclear NMR spectra data in C6D6 or C6D5CD3 for each of 5-10. 相似文献
82.
The X-ray crystal structures of a series of lithium quinolates – lithium 8-hydroxyquinolinate (Liq), lithium 2-methyl-8-hydroxyquinolinate (MeLiq), and 2-phenyl-8-hydroxquinolinate (PhLiq), are compared. The substitution at the 2-position of the 8-hydroxyquinoline ligand has significant impact on the aggregation of the lithium complex in the crystalline state. Liq and MeLiq molecules crystallize as hexamers, whereas PhLiq crystallizes as a tetramer. The possible influence of crystal-packing forces on the preferred cluster structure was probed using density functional theory calculations on a systematically varied set of Liq, MeLiq, and PhLiq clusters. For Liq and MeLiq, the observed structures match the most stable computed structures. In the PhLiq case, the observed tetrameric structure is computed to be less stable (+1.2 kcal/mol/monomer) than the lowest energy structure, a hexamer. In this case, solid-state effects probably outweigh small differences in cluster stability. 相似文献
83.
The new [Li(DME)3+] salt of the previously-known tetra(tert-butyl)erbate(III) anion [Er(t-Bu)4−] has been prepared and structurally characterized. The erbium(III) center is ligated by four tert-butyl groups in an approximately tetrahedral arrangement. The C–Er–C angles between the tert-butyl groups range from 108.8(3)° to 111.2(3)° and the Er–C distances range from 2.352(6) to 2.395(6) Å. The lithium cation is surrounded by three DME molecules, which form a distorted octahedral coordination sphere. Attempts to oxidize the analogous terbate complex [Li(DME)3][Tb(t-Bu)4] and its cerium analog to electrically neutral tetra(alkyl)lanthanide(IV) compounds are described. 相似文献
84.
Syntheses and Structures of Trilithium Cyclotriphosphazenates Equipped with 2‐Halo‐aryl Substituents
Hexakis (2‐halo‐anilino) cyclotriphosphazenes (2‐X‐C6H4NH)6P3N3 {X = F ( 1d ), Cl ( 1e ), Br ( 1f )} were prepared by refluxing mixtures of hexachloro cyclotriphosphazene, 2‐haloaniline and triethylamine in toluene and characterized by single crystal X‐ray diffraction. 1d , 1e and 1f were reacted with nBuLi in thf. Reactions were monitored with 31P NMR. Addition of three equivalents of nBuLi yields lithium complexes of trianionic phosphazenates [{(thf)2Li}3{(2‐X‐C6H4N)3(2‐X‐C6H4NH)3P3N3}] {X= F ( 2d ), Cl ( 2e ) and Br ( 2f )}. 2d , 2e and 2f were structurally characterized by X‐ray diffraction, which reveals monomeric cis‐metalated phosphazenates featuring central P3N3 ring systems of chair conformation. Lithium ions reside in three N(eq)‐P‐N(endo) chelation sites at one face of the P3N3 ring system. Li…X distances are rather long (> 3Å) indicating no Li‐X interactions. 相似文献
85.
Syntheses and Crystal Structures of [Pd9As8(PPh2)8] and [Pd9Sb6(PPh3)8] [PdCl2(PPh3)2] reacts with As(SiMe3)3 to give the new cluster [Pd9As8(PPh3)8] ( 4 ). 4 has been characterized by X-ray crystal structure analysis. It is a molecule in which four [Pd2(PPh3)2]-units are bridged by As2-units. A further Pd atom is located in the centre of the cluster. 4 crystallizes in the space group C2/c with four formula units per unit cell. The lattice constants at 200 K are: a = 3 970.6(3), b = 1 648.90(16), c = 3 266.30(20) pm, β = 131,44(4)°. The reaction of [PdCl2(PPh3)2] with Sb(SiMe3)3 yields [Pd9Sb6(PPh3)8] ( 5 ). 5 consists of a body centred cubic Pd9-cluster. All of the cube faces are capped by μ4-Sb-ligands. 5 crystallizes in the space group Pn3 with two formula units per unit cell. The lattice constants at 200 K are: a = b = c = 1 995.4(2) pm. 相似文献
86.
Fluoridolysis of Diphosphoryl Compounds The behaviour of diphosphoryl compounds [X2(O)P]2Y in fluoridolysis reactions is decisively determined by the nature of the bridging group Y. In the cases of Y = NH and CH2 and X = Cl [F2P(O)]2N? and [F2P(O)]2CH2 are obtained quantitatively. For Y = NPh, O, and CH2 the formation of phosphorylated pentafluorophosphates [F5P? Y? POX2]? is observed. Amido and ester derivatives containing fluorine (see table 2) are obtained from the corresponding chloro compounds by Cl/F exchange. Fluoridolysis of the azadiphosphetidine 19 results in the formation of acyclic 19 a . 相似文献
87.
Hüseyin Göktepe 《中国化学会会志》2013,60(2):218-222
Dy doping and carbon coating are adopted to synthesize a LiFePO4 cathode material in a simple solution environment. The samples were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Their electrochemical properties were investigated by cyclic voltammetry (CV) and galvanostatic charge‐discharge tests. An initial discharge capacity of 153 mAh/g was achieved for the LiDy0.02Fe0.98PO4/C composite cathode with a rate of 0.1 C. In addition the electronic conductivity of Dy doped LiFePO4/C was enhanced to 1.9 × 10?2 Scm?1. The results suggest that the improvement of the electrochemical properties are attributed to the dysprosium doping and carbon coating which facilitates the phase transformation between triphylite and heterosite during cycling. XRD data indicate that doping did not destroy the lattice structure of LiFePO4. To evaluate the effect of Dy substitution, cyclic voltammetry was used at room temperature. prepared. From Cv measurement a more symmetric curve with smaller interval between the cathodic and anodic peak current was obtained by Dy substitution. This denoted a decreasing of polarization with Dy substitution, which illustrated an enhancement of electrochemical performances. 相似文献
88.
Zucheng Wu Ying Sing Fung 《International journal of environmental analytical chemistry》2013,93(7):431-442
The preconcentration technique of purge-and-trap has been investigated in the present work for quantitative adsorption of volatile organic pollutants purged from water samples. A dynamic purging device with variable volume size has been constructed and tested to purge different concentrations of organic compounds. With Tenax GR as the adsorbent, a dynamic purge-and-trap technique was developed combining on-column preconcentration procedures using ambient trapping/thermal desorption/cryogenic focusing/back-flash injection prior to separation and determination using capillary gas chromatography. Various aromatic compounds in water were determined, giving linear working ranges over five orders of magnitude from 0.02 to 5000 µg/L. The analytical procedures were optimized under the assistance of ultrasonication with results validated for the determination of organic contaminants in underground water and tap water, giving over 93% recoveries and a detection limit of 0.01 µg/L, two orders of magnitude lower than those obtained using commercial available instruments with on-line configuration to minimize cross-contamination. The technique provides a potential automated method for in situ monitoring of volatile organic compounds in water. 相似文献
89.
Nahar Singh Rama Devi Ramachandran Ajit Kumar Sarkar 《International journal of environmental analytical chemistry》2013,93(10):891-896
Silica is removed from fly ash sample by hydroflourination for its effective determination gravimetrically and the remaining residue is subjected to lithium tetraborate (Li2B4O7) fusion followed by dissolution in dilute nitric acid to obtain a clear solution in which elements including aluminum (Al), iron (Fe), calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu) and zinc (Zn), have been determined by Flame Atomic Absorption Spectrometry (FAAS). Two fly ash samples analyzed by the proposed method have been received from the National Council of Cement and Building Materials (NCCBM), India (proposed CRM in future) and fly ash CRM 1633 (b) from NIST, USA. The validity of the method has been established by analyzing fly ash CRM 1633 (b) as reference standard. The standard deviation has been calculated for each measurement. 相似文献
90.
Majid M. Heravi Nasrin Farhangi Yahya Sh. Beheshtiha Karim Assadolah Mitra Ghassemzadeh Koroush Tabar-Hydar 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):2883-2885
In an environmentally benign system, alcohols are rapidly oxidized to carbonyl compounds using CrO 3 supported onto wet silica gel as an oxidant under microwave irradiation. 相似文献