Cleavage of the Fe—Fe Bond of （Me2SiSiMe2） [η^5－C5H4Fe（CO）2]2 with Na／Hg and Molecular Structure of the Ring－Opened Complex

The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain.     

镓在裸Si系和SiO2/Si系掺杂效应

Based on the diffusion action of gallium in silicon and SiO2 ,a diffusion model of gallium doping in bare silicon system and SiO_2/Si system is first presented in this paper ,the gallium doping effect in the two systems is analyzed theoretically. Experiments and applications have proved that the use of the open-tube gallium deffusion in SiO2/Si system can substantially improve diffusion quality and device characteristics .     

Nonclassical titanocene silyl hydrides

The titanocene silyl hydride complexes [Ti(Cp)2(PMe3)(H)(SiR3)] [SiR3=SiMePhCl (6), SiPh2Cl (7), SiMeCl2 (8), SiCl3 (9)] were prepared by HSiR3 addition to [Ti(Cp)2(PMe3)2] and were studied by NMR and IR spectroscopy, X-ray diffraction (for 6, 8, and 9), and DFT calculations. Spectroscopic and structural data established that these complexes exhibit nonclassical Ti-H-Si-Cl interligand hypervalent interactions. In particular, the observation of silicon-hydride coupling constants J(Si,H) in 6-9 in the range 22-40 Hz, the signs of which we found to be negative for 8 and 9, is conclusive evidence of the presence of a direct Si-H bond. The analogous reaction of [Ti(Cp)2(PMe3)2] with HSi(OEt)3 does not afford the expected classical silyl hydride complex [Ti(Cp)2(PMe3)(H)[Si(OEt)3]], and instead NMR-silent titanium (apparently TiIII) complex(es) and the silane redistribution product Si(OEt)4 are formed. The structural data and DFT calculations for the compounds [Ti(Cp)2(PMe3)(H)(SiR3)] show that the strength of interligand hypervalent interactions in the chlorosilyl complexes decreases as the number of chloro groups on silicon increases. However, in the absence of an Si-bound electron-withdrawing group trans to the Si-H moiety, a silane sigma complex is formed, characterized by a long Ti-Si bond of 2.658 A and short Si-H contact of 1.840 A in the model complex [Ti(Cp)2(PMe3)(H)(SiMe3)]. Both the silane sigma complexes and silyl hydride complexes with interligand hypervalent interactions exhibit bond paths between the silicon and hydride atoms in Atoms in Molecules (AIM) studies. To date a classical titanocene phosphane silyl hydride complex without any Si-H interaction has not been observed, and therefore titanocene silyl hydrides are, depending on the nature of the R groups on Si, either silane sigma complexes or compounds with an interligand hypervalent interaction.     

Ceramic Foams from a Preceramic Polymer and Polyurethanes: Preparation and Morphological Investigations

Open-cell ceramic foams were obtained from a preceramic polymer (silicone resin) and blown polyurethanes. The preceramic polymer, which is crosslinked by condensation of silanol groups, was dissolved in CH2Cl2 and added to a liquid polyol containing the surfactant and the amine catalyst. Isocyanate was then added to the mixture and the foam was obtained through a twofold blowing mechanism (physical and chemical blowing). The morphology of the expanded polyurethane, which can be flexible or semirigid, characterized the final structure of the ceramic foam. The materials obtained were pyrolyzed in a nitrogen flux at temperatures of 1000–1200°C, thus allowing for the polymer-to-ceramic transformation to occur in the preceramic polymer. The ceramic foams produced in this way consisted of an amorphous silicon oxycarbide ceramic (SiOC). They presented a density ranging from 0.1 to 0.3 g/cm3. The average pore diameter ranged from 200 to 400 m and they possessed 80 to 90% open porosity.     

New metal-rich mixed chalcogenides with an intergrowth structure: Ni<Subscript>5.68</Subscript>SiSe<Subscript>2</Subscript>, Ni<Subscript>5.46</Subscript>GeSe<Subscript>2</Subscript>, and Ni<Subscript>5.42</Subscript>GeTe<Subscript>2</Subscript>

New metal-rich mixed nickel-silicon and nickel-germanium chalcogenides, Ni_5.68SiSe₂, Ni_5.46GeSe₂, and Ni_5.42GeTe₂, were synthesized by high-temperature ceramic techniques. The X-ray diffraction study of single crystals grown from a molten flux revealed that the compounds are isostructural and crystallize in the tetragonal system (space group I4/mmm, Z = 2). These compounds are the first members of the family of M_7−δEX₂-type (M = Ni or Pd; E = Sn or Sb; X is chalcogen) intergrowth structures containing “light” p elements E. Resistivity measurements on pressed textured pellets showed that both selenides are anisotropic metallic conductors in the directions parallel and perpendicular to the heterometallic bond systems. The geometric criteria of stability of the intergrowth structure type under consideration are discussed. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1632–1638, September, 2007.     

Combined IR and XPS analysis of the native (1 0 0) surface of single‐crystalline silicon after HFaq etching

A combined analysis, based on angle‐resolved X‐ray photoelectron spectroscopy and multiple‐internal‐reflection infrared spectroscopy, of the (1 0 0) silicon surface after etching in dilute aqueous solution of HF is presented. The analysis shows that the surface is mainly formed by a heterogeneous distribution of SiH, SiH₂ and SiH₃ terminations, but contains (in addition to sub‐stoichiometric oxidized silicon) a form of reduced silicon, not consistent with the currently accepted picture of the native HF_aq‐etched surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Tetraaryl-methane analogues in group 14—V. Distortion of tetrahedral geometryin terms of through-space π–π and π–σ interactions andNMR sagging in terms of π–σcharge transfer

44 members of thecompound series Ph_4−nMR_n (M=Si, Ge, Sn, Pb; R=o-, m-, p-Tol; n=0–4) were synthesized (15 newcompounds). The crystal structures of Ph₃Sn (o-Tol) and PhSn (o-Tol)₃ were determined and compared to 16 known structures. Subject to the distanced (M–C), an interplay between through-space π–π repulsion and π–σ attraction leads to either elongated or compressed tetrahedral geometry. ²⁹ Si-, ¹¹⁹ Sn- and ²⁰⁷ Pb-NMR chemical shifts were determined in solution and in the solid state. ⁷³ Ge chemical shifts were measured only in solution. Anupfield or downfield sagging of the chemical shifts along each series is rationalized in terms of a π–σcharge transfer which is constrained by torsion of the aromatic groups.     

阳极氧化与超临界干燥结合制备多孔硅

多孔硅（PS）在室温下发射强可见光，这一发现在国际上引起极大关注，成为材料科学、半导体物理和化学以及信息科学领域研究的热点［1，2］．最近三、四年，国内外对PS制备工艺、影响PS发光的因素、PS发光机制、PS应用前景等方面进行了广泛的研究［2］，但有一些基本问题仍待解决，如关于PS发光机制尚存在分歧；PS电致发光效率低，离应用差距甚远；高多孔度PS微孔结构不稳定等．PS微孔内溶剂蒸发过程中，由于毛细管张力的存在，造成微孔骨架受力不匀．强的应力使PS骨架脆弱，甚至微孔结构坍缩，从而导致PS结构不稳定．对于高多孔度…     

Electrostatic Interactions Leading to Hierarchical Interpenetrating Electroconductive Networks in Silicon Anodes for Fast Lithium Storage

Recently, the frequency of combining MXene, which has unique properties such as metal-level conductivity and large specific surface area, with silicon to achieve excellent electrochemical performance has increased considerably. There is no doubt that the introduction of MXene can improve the conductivity of silicon and the cycling stability of electrodes after elaborate structure design. However, most exhaustive contacts can only improve the electrode conductivity on the plane. Herein, a MXene@Si/CNTs (HIEN-MSC) composite with hierarchical interpenetrating electroconductive networks has been synthesized by electrostatic self-assembly. In this process, the CNTs are first combined with silicon nanoparticles and then assembled with MXene nanosheets. Inserting CNTs into silicon nanoparticles can not only reduce the latter‘s agglomeration, but also immobilizes them on the three-dimensional conductive framework composed of CNTs and MXene nanosheets. Therefore, the HIEN-MSC electrode shows superior rate performance (high reversible capacity of 280 mA h⁻¹ even tested at 10 A g⁻¹), cycling stability (stable reversible capacity of 547 mA h g⁻¹ after 200 cycles at 1 A g⁻¹) and applicability (a high reversible capacity of 101 mA h g⁻¹ after 50 cycles when assembled with NCM622 into a full cell). These results may provide new insights for other electrodes with excellent rate performance and long-cycle stability.