Pt羰基簇合物在NaY内的合成机理

利用IR，EXAFS, ~(13)CO同位素交换反应及与NO作用等手段研究了Pt羰基簇合物[Pt_3(CO)_6]~(2-)_n(n＝3,4)在NaY分子筛超笼内的合成机理．在氧化样品Pt~(2+)/NaY上300－373 K的还愿羰基化过程中，首先Pt~(2+)与CO反应生成PtO(CO)物种(波数σ_(CO)＝2110 cm~(-1))，然后聚集成“Pt_3(CO)_6”(σ_(CO)＝2112，1896和1841 cm~(-1))，最后生成深绿色的Pt羰基簇合物Pt_(12)(CO)_(24)]~(2-)/NaY(σ_(CO)＝2080，1824 cm~(-1))．“Pt_3(CO)_6”的羰基在室温下能迅速地与~(13)CO发生交换，而[Pt_3(CO)_6]~(2-)_n(n＝3,4)的羰基与~(13)CO的同位素交换即使在343 K也进行得很慢，室温下，NO能逐步破坏Pt羰基簇合物的层间和层内Pt－Pt键，得到中间物种“Pt_3(CO)_6”和PtO(CO)，同时在气相产生CO_2和N_2O．而由上述两中间物种出发，300－353 K温度下，在CO气氛中的还原羰基化又能可逆地得到原羰基簇合物．     

Biradicals/zwitterions from thermolysis of enyne-isocyanates. Application to the synthesis of 2(1H)-pyridones, benzofuro[3,2-c]pyridin-1(2H)-ones, 2,5-dihydro-1H-pyrido[4,3-b]indol-1-ones, and related compounds

Thermolysis of benzannulated enyne-isocyanates 13 and enyne-isocyanates 36 and 37 promoted the cycloaromatization reactions to generate in situ O,4-didehydro-2-hydroxyquinolines and O,4-didehydro-2-hydroxypyridines, respectively, as reactive intermediates. These cycloaromatized intermediates could be captured either as biradicals and/or as zwitterions depending on the nature of the substituent at the alkynyl terminus. The intermediate derived from cycloaromatization of 13a bearing a phenyl substituent could be regarded as biradical 14, which then abstracts hydrogen atoms from gamma-terpinene leading to 2(1H)-quinolinone 15. Alternatively, the same intermediate could also be regarded as zwitterion 14', which then undergoes an initial hydride abstraction from gamma-terpinene followed by protonation to produce 15. The presence of a 2-phenylethyl substituent in 13b and 37a or a 2-methylphenyl substituent in 37b also allowed the resulting intermediates to be captured intramolecularly either as biradicals or as zwitterions, producing 2(1H)-quinolinone 19, 2(1H)-pyridone 39, and benzopyranopyridine 43, respectively. On the other hand, with a 2-methoxyphenyl, a 2-(dimethylamino)phenyl, or a 3-methoxypropyl substituent, the chemical behavior of the cycloaromatized adduct could be best accounted for in terms of a zwitterionic intermediate leading to benzofuro[3,2-c]quinolin-6(5H)-one (20), 5,11-dihydro-11-methyl-6H-indolo[3,2-c]quinolin-6-one (25), benzofuro[3,2-c]pyridin-1(2H)-one 44, 2,5-dihydro-2,5-dimethyl-1H-pyrido[4,3-b]indol-1-one 46, and related compounds. Interestingly, thermolysis of 37f bearing a 2-(methoxymethyl)phenyl substituent at the alkynyl terminus produced the unexpected benzopyranopyridine 56 as the major product in a process involving the cleavage of the bond between the methoxyl oxygen and the adjacent methylene carbon. The efficiency and selectivity of the cycloaromatization reaction could also be enhanced by the introduction of 1.1 to 10 equiv of dimethylphenylsilyl chloride to the reaction mixture to capture the resulting zwitterion.     

Synthesis of 7,9-dideoxybaccatin IV analogs from sinenxan A

Sinenxan A, a taxoid isolated from callus tissue cultures of Taxus yunnanensis was converted into 13-oxo-7,9-dideoxy-2-debenzoyl-2-acetyl-baccatin IV and 7,9-dideoxy-2-debenzoyl-4-deacetyl-baccatin IV, a key framework of 1,7,9-trideoxypaclitaxel. Several special steps in this transformation are worthy of note: (1) deoxygenation by treatment with hypophosphorous acid at C-14 position; (2) a highly regioselective O-deacetylation of taxanes at C-5 position; and (3) stereoselective reduction of the 13-carbonyl group by transannular assistance from the C-4-hydroxyl.     

Synthesis, spectroscopic studies and crystal structure of a polyoxoanion cluster incorporating para-bromophenylimido ligand, (Bu4N)2[Mo6O18(NC6H4Br-p)]

An organic-inorganic hybrid compound, (Bu₄N)₂[Mo₆O₁₈(NAr)] (Ar = p-BrC₆H₄) has been synthesized via the DCC dehydrating protocol of the reaction of [α-Mo₈O₂₆]⁴⁻ with 4-bromoaniline hydrochloride in anhydrous acetonitrile, which has been characterized by UV-Vis spectra, ¹H NMR and single crystal X-ray diffraction study. By comparing the UV-Vis spectra, which were used to monitor the reaction, the optimum preparative condition for this compound was also determined. This compound crystallizes in the monoclinic space group P2₁/n, which is featured in a terminal para-bromophenylimido group linked to an Mo atom of a hexamolybdate cluster by a Mo-N triply bond. In addition, there are π-π dimerization of the neighboring cluster anions though the parallel aromatic rings in their crystals.     

Ternary surface complexes by theE(%)-pH curve method

A new method for the study of ternary surface complexes at liquid-solid interface, theE(%) -pH curve method, was proposed. Four types ofE(%)-pH curves, namely, phenomenon of left-right shifts of S-shaped curve, V-shaped curve, monodirection shift curve and X-shaped curve, were discovered. Correspondingly, apart from type (I) ternary surface complex and type (II) ternary surface complex , a new type of ternary surface complex was discovered. Project supported by the National Natural Science Foundation of China and the Fund of Doctoral Degree’s Spot.     

ATR-FTIR study of Bacillus sp. and Escherichia coli settlements on the bare and Al2O3 coated ZnSe internal reflection element

FTIR-ATR has been used for understanding the interaction between bacteria and surfaces in the adsorption progress.     

A Novel Polyoxovanadium Cluster Shell: β‐As8V14O42

The hydrothermal reaction of VOSO₄, As₂O₅, piperazine and H₂O produces [H₂N(CH₂)₄NH₂]₄[β‐As₈V₁₄O₄₂(SO₄)]·2HSO₄ ( 1 ), which is the first arsenic‐vanadium cluster containing a spherical β‐As₈V₁₄O₄₂ shell. The structure of this compound was characterized by single crystal X‐ray diffraction, elemental analysis, TG, and IR spectrum. Crystal data for 1 : Orthorhombic, Cmcm, a = 15.369(1) Å, b = 16.404(1) Å, c = 25.772(1) Å, V = 6497.4(9) ų, Z = 4.     

Solvent extraction of uranium(VI) with benzyloctadecyldimethylammonium chloride (BODMAC) from highly concentrated chloride solution

The ²²²Rn emanation fraction (EF) released from the technically enhanced naturally occurring radioactive material (TE-NORM) wastes at certain sites of petroleum and gas production was determined. The samples were analyzed by γ-ray spectrometry to determine the activity concentration of the ²²⁶Ra content, of which the ²²²Rn emanation fraction was calculated. The results showed that the ²²²Rn emanation fraction differs in the oil and gas production sites and it is independent of the activity concentration of ²²⁶Ra. This revised version was published online in August 2006 with corrections to the Cover Date.     

Theoretical study of the local structure and Raman spectra of CaO-SiO2 binary melts

A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson's GF matrix method for the calculations of eigenfrequencies and corresponding vectors, electro-optical parameters method (EOPM) for the Raman intensity calculations, and the bond polarizability model (BPM) for the determination of polarizability and polarizability derivative. One of the most important characteristics of this procedure is the achievement of the partial Raman spectra of five tetrahedral units, as well as the total spectral envelope. In this paper, the calculation was carried out for the vitreous and molten calcium silicates with different compositions and at various temperatures. It is worthwhile to note that the calculation is based on statistical configurations distribution in the space and so it is not needed to artificially adjust the full width at half maximum (FWHM) of spectra. It was also tested through the good agreement of the calculated spectra with the experimental, including some regularity of spectral properties. According to the calculation, the symmetrical stretching of whole tetrahedral units, to which the stretching of Si-O(nb) bond gives the main contribution to intensity, is proven to be the dominance in the high-frequency range (800-1200 cm(-1)) and the symmetrical bending of Si-O(b)-Si, to which the stretching of Si-O(b) bond exhibits the main contribution, is the dominance in the medium-frequency range (400-700 cm(-1)). As the first theoretical results, the Raman scattering coefficient of each Q(i) was found little change along with the variation of composition and temperature.     

立体化学刚性的七配位环戊二烯基三(二苄基二硫代氨基甲酸)钛、锆、铪配合物的合成和性质

二烷基二硫代氨基甲酸基作为良好的双齿配体较易与过渡金属生成高配位的配合物,含有环戊二烯基的高配位钛、锆、铪配合物的研究相继出现^[1-5],这类七配位、18-电子构型的配合物是立体化学刚性,具有独特的光谱性质和结构行为。选择钛、锆和铪二茂二氯化物与三当量的二苄基二硫代氨基甲酸钠反应合成了五种未见报道的七配位配合物,讨论了产物的光谱性质和配位结构。