Closely Approaching the Silylium Ion (R3Si+)

The crystal structure of the tri-isopropyl silyl species, i-Pr(3)Si(Br(6)-CB(11)H(6)), where the brominated carborane Br(6)-CB(11) H(6)(-) is perhaps the least nucleophilic anion presently known, has revealed the highest degree of silylium cation character (R(3)Si(+)) yet observed. The average C-Si-C angle is 117 degrees , only 3 degrees short of the planarity expected of a pure silylium ion(120 degrees ). This value compares to 114 degrees recently reported for a toluene-solvated silyl cation, [Et(3)Si(toluene)](+) by Lambert and co-workers. The greater silylium ion character of i-Pr(3)Si(Br(6)-CB(11)H(6)) versus [i-Pr(3)Si(toluene)](+) is also reflected in the larger downfield shift of the silicon-29 nuclear magnetic resonance, 109.8 versus 相似文献   

Experimental detection of tetranitrogen

Tetranitrogen (N4), which has been the subject of great theoretical interest, has been prepared from the N4+ cation and positively detected as a gaseous metastable molecule with a lifetime exceeding 1 microsecond in experiments based on neutralization-reionization mass spectrometry. An examination of the geometry of N4+ and the fragmentation pattern of the (14)N2(15)N2 neutral molecule has revealed that the latter is characterized by an open-chain geometry with two distinct, closely bound N2 units joined by a longer weaker bond.     

The (Me5C5)Si+ cation: a stable derivative of HSi+

The reaction of decamethylsilicocene, (Me5C5)2Si, with the proton-transfer reagent Me5C5H2+B(C6F5)4- produces the salt (Me5C5)Si+ B(C6F5)4(2), which can be isolated as a colorless solid that is stable in the absence of air and moisture. The crystal structure reveals the presence of a cationic pi complex with an eta5-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The 29Si nuclear magnetic resonance at very high field (delta = - 400.2 parts per million) is typical of a pi complex of divalent silicon. The (eta5-Me5C5)Si+ cation in 2 can be regarded as the "resting state" of a silyliumylidene-type (eta1-Me5C5)Si+ cation. The availability of 2 opens new synthetic avenues in organosilicon chemistry. For example, 2 reacted with lithium bis(trimethylsilyl)amide to give the disilene E-[(eta1-Me5C5)[N(SiMe3)2]Si]2(3).     

Spectroscopic evidence for pressure-induced coordination changes in silicate glasses and melts

Infrared spectra demonstrate that at pressures above 20 gigapascals and room temperature the regular tetrahedral coordination of oxygen around both silicon and aluminum ions is severely disrupted in SiO(2), CaMgSi(2)O(6), and CaAlSi(2)O(8) composition glasses. The spectra are consistent with gradual, pressure-induced increases in the coordination numbers of silicon and aluminum. A variety of coordination environments, from sixfold to fourfold, appears to be present at pressures as high as about 40 gigapascals. This apparent change in coordination is not quenchable at room temperature: on decompression, the glasses return to tetrahedral coordination. This continuous and reversible coordination change in amorphous silicates explains the lack of observation of coordination changes in silicate glasses quenched from high pressure, the shallow melting slopes observed for mantle silicates at high pressures, and the possible presence of neutrally buoyant magmas deep within the terrestrial planets.     

Crystal Chemistry of Silicon--Oxygen Bonds at High Pressure: Implications for the Earth's Mantle Mineralogy

Transformations involving a change from tetrahedrally coordinated to octahedrally coordinated silicon ((IV)Si --> (VI)Si) are observed to occur at high pressure when the mean (IV)Si-O bond compresses to approximately 1.59 angstroms based on known room-pressure crystal structures, Si-O bond compressibilities, and pressures of (IV)Si --> (VI)Si transformations. The lower two-thirds of the mantle transition zone of high-density gradient (500 to 900 kilometers) corresponds to the predicted range of (IV)Si --> (VI)Si transformations. The 10 percent density increase of this zone at zero pressure is attributed primarily to the density increase associated with the change in silicon coordination. Below 900 kilometers all silicon is predicted to be in octahedral or greater coordination. The concept of cation polyhedral stability fields is defined.     

A planar rhombic charge-separated tetrasilacyclobutadiene

The cyclobutadiene (CBD) molecule C(4)H(4) deviates from a high-symmetry square geometry to compensate for its antiaromatic electronic structure. Here, we report a CBD silicon analog, Si(4)(EMind)(4) (1), stabilized by the bulky 1,1,7,7-tetraethyl-3,3,5,5-tetramethyl-s-hydrindacen-4-yl (EMind) groups, obtained as air- and moisture-sensitive orange crystals by the reduction of (EMind)SiBr(3) with three equivalents of lithium naphthalenide. X-ray crystallography reveals a planar and rhombic structure of the Si(4) four-membered ring, with alternating pyramidal and planar configurations at the silicon atoms. The large (29)Si chemical shift differences (Δδ > 350 parts per million) in the solid-state nuclear magnetic resonance spectra suggest a contribution of an alternately charge-separated structure. The rhombic-shaped charge-separated singlet state of compound 1 thus stabilizes its cyclic 4π-electron antiaromaticity in a manner that contrasts sharply with the bond-length alternation, characterizing the rectangular distortion of carbon-based CBD.     

A stable silicon(0) compound with a Si=Si double bond

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si-Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 +/- 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si-Si(Cl):L and L:Si=Si:L.     

Crystallographic evidence for a free silylium ion

Evidence for a three-coordinate silyl cation is provided by the crystal structure of [(Mes)3Si][H-CB11Me5Br6].C6H6 (where Mes is 2,4,6-trimethylphenyl). Free (Mes)3Si+ cations are well separated from the carborane anions and benzene solvate molecules. Ortho-methyl groups of the mesityl substituents shield the silicon atom from the close approach of nucleophiles, while remaining innocent as significant ligands themselves. The silicon center is three-coordinate and planar. The downfield 29Si nuclear magnetic resonance chemical shift in the solid state (226.7 parts per million) is almost identical to that in benzene solution and in "gas phase" calculations, indicating that three-coordination can be preserved in all phases.     

Photoinduced electron transfer from a conducting polymer to buckminsterfullerene

Evidence for photoinduced electron transfer from the excited state of a conducting polymer onto buckminsterfullerene, C(60), is reported. After photo-excitation of the conjugated polymer with light of energy greater than the pi-pi* gap, an electron transfer to the C(60) molecule is initiated. Photoinduced optical absorption studies demonstrate a different excitation spectrum for the composite as compared to the separate components, consistent with photo-excited charge transfer. A photoinduced electron spin resonance signal exhibits signatures of both the conducting polymer cation and the C(60) anion. Because the photoluminescence in the conducting polymer is quenched by interaction with C(60), the data imply that charge transfer from the excited state occurs on a picosecond time scale. The charge-separated state in composite films is metastable at low temperatures.     

Metal ion activation of phosphate transfer by bidentate coordination

The hydrolysis of methyl phosphate bound to the triethylenetetramine-cobalt(III) ion is much faster than the hydrolysis of either dimethyl phosphate bound to the same cation or methyl phosphate bound to the pentamminecobalt-(III) ion. The rate enhancement is attributed to bidenate coordination of the methyl phosphate. This feature suggests a pseudorotation mechanism analogous to that proposed by Westheimer for the hydrolysis of ethylene methyl phosphate. Stabilization of bidentate coordination might play a role in metal ion activation of phosphate-transfer enzymes.     

Silver-catalyzed C-C bond formation between methane and ethyl diazoacetate in supercritical CO₂

Even in the context of hydrocarbons' general resistance to selective functionalization, methane's volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH(4)) with ethyl diazoacetate (N(2)CHCO(2)Et) to yield ethyl propionate (CH(3)CH(2)CO(2)Et). The use of supercritical carbon dioxide (scCO(2)) as the solvent is key to the reaction's success. Although the catalyst is only sparingly soluble in CH(4)/CO(2) mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.     

Dissociation of individual molecules with electrons from the tip of a scanning tunneling microscope

The scanning tunneling microscope (STM) can be used to select a particular adsorbed molecule, probe its electronic structure, dissociate the molecule by using electrons from the STM tip, and then examine the dissociation products. These capabilities are demonstrated for decaborane(14) (B(10)H(14)) molecules adsorbed on a silicon(111)-(7 x 7) surface. In addition to basic studies, such selective dissociation processes can be used in a variety of applications to control surface chemistry on the molecular scale.     

己酸二乙氨基乙醇酯及其盐的合成研究

以己酸与二乙氨基乙醇为原料,强酸性阳离子交换树脂为催化剂,合成出了植物生长调节剂——己酸二乙氨基乙醇酯(DA-6),通过正交试验优化出了其最佳的合成工艺条件:当酸醇物质量之比为1.2:1.0,催化剂用量为1.7%,带水剂为甲苯时,产物的收率可达93.5%,产品纯度95.0%。此外还探索了DA-6盐的制备条件。     

柔嫩艾美耳球虫甘肃株抗药性的试验研究

用柔嫩艾美耳球虫甘肃株(E.tenella G S,E t G S)对15日龄雏鸡进行感染,以最适抗球虫活性百分率、抗球虫指数、相对卵囊产量和病变记分减少率为指标,进行综合评定,研究了该虫株对三九球痢灵、地克珠利、氯苯胍和地克珠利氯苯胍合剂等几种常用抗球虫药的敏感性。结果表明,该虫株对三九球痢灵有中度抗药性,对地克珠利和地克珠利氯苯胍合剂有轻度抗药性,对氯苯胍无抗药性。     

Picometer-scale electronic control of molecular dynamics inside a single molecule

Tunneling electrons from a low-temperature (5 kelvin) scanning tunneling microscope were used to control, through resonant electronic excitation, the molecular dynamics of an individual biphenyl molecule adsorbed on a silicon(100) surface. Different reversible molecular movements were selectively activated by tuning the electron energy and by selecting precise locations for the excitation inside the molecule. Both the spatial selectivity and energy dependence of the electronic control are supported by spectroscopic measurements with the scanning tunneling microscope. These experiments demonstrate the feasibility of controlling the molecular dynamics of a single molecule through the localization of the electronic excitation inside the molecule.     

含硅、钙土壤调酸剂应用于酸性水稻土的效果分析

连续两季施用含硅、钙土壤调酸剂,对湖北省水稻产区酸性水稻土基本理化性状和水稻产量进行评价。结果表明,施用不同量的含硅、钙土壤调酸剂对土壤的pH均有提高,提高值最高达0.29;土壤硅铝率提高0.23;对土壤阳离子交换量也有一定影响,增加幅度最高达1.90 cmol(+)/kg;对水稻结实率提高幅度达5.56%,千粒重增加0.73 g;对土壤容重及耕层有机质、全氮、碱解氮、有效磷等影响不大。表明在酸性较重土壤中施用含硅、钙土壤调酸剂可以改善土壤酸性、硅铝率和提高阳离子交换量,对土壤结构和其他养分含量影响不明显,对水稻增产效果明显。     

夜间增温下施硅对稻田CH4好氧氧化及其氮响应的影响

【目的】研究硅肥对增温稻田甲烷(CH₄)好氧氧化速率的影响效应,为探索未来全球变暖背景下稻田温室气体减排措施提供科学依据。【方法】采用田间开放式增温系统对稻田土壤进行夜间增温,共设4个处理：夜间常温不施硅(CK)、夜间增温不施硅(NW)、夜间常温施硅(Si)和夜间增温施硅(NW+Si)。采集上述处理4年后的耕层根际土和非根际土,在无氮添加和氮添加(NH₄⁺、NO₃^-和尿素)条件下进行室内培养,采用¹³CH₄标记方法,研究稻田CH₄好氧氧化速率和固碳特征及其对氮肥的响应。【结果】Si处理稻田土壤的总有机碳和水溶性有机碳含量分别为23.2 g/kg和216.7 mg/kg,较CK稻田提高10.5%和26.7%;而NW处理的总有机碳和水溶性有机碳则分别较CK稻田降低11.9%和9.9%。施硅处理(Si和NW+Si)根际土的CH₄好氧氧化速率显著高于不施硅处理(CK和NW)(P<0.05),其...     

用二氧化硅聚氨酯涂料改良木材表面性质的研究

为了解二氧化硅（SiO2）对涂料的影响,将粉状SiO2加入聚氨酯涂料中,并涂饰于马尾松木材表面,以达到改良木材表面性质的目的。结果表明:利用硅烷偶联剂KH 570在甲苯溶剂中改性的SiO2的疏水亲油性增强,其在聚氨酯涂料中的分散性优于未改性SiO2;SiO2在一定程度上提高了木材表面漆膜的性能,漆膜的耐冲击性、抗老化性能得到显著提高;加入改性SiO2的聚氨酯涂料性能在耐磨性、硬度、耐冲击性、耐老化性方面优于未改性SiO2聚氨酯涂料。通过将SiO2增强体添加到聚氨酯涂料中,增强了涂料的性能,表明SiO2与聚氨酯具有较好的协同作用。      

X-ray line and continuum spectra of solar flares from 0.5 to 8.5 angstroms

Two crystal spectrometers aboard the orbiting solar observatory OSO-4 cover the wavelength ranges 0.5 to 3.9 angstroms and 1.0 to 8.5 angstroms. Within this range, there appear emission lines from hydrogen-like and helium-like states of calcium, sulfur, silicon, magnesium, and aluminum. The Mg XII Lyman-alpha is present strongly in all x-ray flares. The most intense flares (such as class 3) produce strong Si XIV Lyman-alpha and often S XVI Lyman-alpha. Emission, in the form of Ka lines of highly ionized states of calcium, iron, aluminum, and silicon is usually present. The continuum from 1 to 10 angstroms always dominates the line emission by more than an order of magnitude. Electron temperatures derived from the slope of the continuum spectrum are in the range of 10(7) to 10(8) degrees K, considerably higher than theoretical ionization equilibrium temperatures.     

Xenon Tetrafluoride: Crystal Structure

On the basis of a three-dimensional x-ray analysis, the xenon tetrafluoride molecule in the solid is planar; the approximate symmetry is D(4h). The average distance between the xenon and the fluorine is 1.92 +/- 0.03 A.