Synthesis, characterization and molecular structure of a novel asymmetrical half-sandwich binuclear iron carborane complex Cp ' Fe-2(2)(CO)(3)(Se2C2B10H10)

The half-sandwich methylcyclopentadlenyl iron carbonyl complex reacted with 1,2-dilithium diselenolate carborane Li2Se2C2B10H10 (1) which was produced by the insertion of element Se into 1, 2-dilithium carborane to give a half-sandwich binuclear iron carborane complex Cp'Fe-2(2)(CO) 3Se2C2B10H10 (3). X-ray structural analysis of complex 3 reveals that one of the iron atoms is chiral.

Dinuclear half-sandwich complexes containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligands. Molecular structures of Cp2Fe2(CO)(3)[mu-Se2C2(B10H10)], Cp2Ru2[mu-S2C2(B10H10)](2), and CP*Ru-2(2)(mu-Se)[mu-Se2C2(B10H10)].

Three prototypes of dinuclear complexes were obtained from the reactions of dilithium 1,2-dicarbacloso-dodecaborane-1,2-dichalcogenolates, (B10H10)C-2-(ELi)(2) (E = S, Se), with CpFe(CO)(2)Cl (1), CpRu(PPh3)(2)Cl (2), or [Cp*RuCl2](2) (3), respectively, and their structures have been determined by X-ray crystallography.

Synthesis and characterization of polynuclear half-sandwich lanthanoid complexes [Na(THF)(6)](2)[(Cp6Sm6Se13)-Sm-t] and [Li(LHF4](2)[Cp6Nd6Se13]

The half-sandwich tert-butyl cyclopentadienyl lanthanoid complexes {[Cp ' Ln(THF)](2)(mu (2)-Cl)(2)(mu (3)-Cl)(3)Na(THF)}(n) [Cp ' = eta (5)-' BuC5H4; Ln = Nd (1a), Sm (1b), Gd (1c), Yb (1d)] are prepared by the reaction of anhydrous lanthanoid trichloride, LnCl(3), with NaCp ' in THF solution. Complex 1b reacts with Na2Se5 to give hexanuclear samarium polyselenide complexes [Na(THF)(6)](2)[Cp-6' SM6(mu (6)-Se)(mu -Se-2)(6)] (2). An analogous cyclopentadienyl neodymium polyselenide complex [Li(THF)(4)](2)[Cp6Nd6(mu (6)-Se)(mu -Se-2)(6)] (3) is synthesized by the reaction of [CpNdCl2. 2LiCl . 5THF] with Na2Se5 in THF solution. The molecular structures of 1a and 2 were determined by X-ray crystal structure analysis. Complex 2 contains an interstitial selenium atom which is coordinated with six samarium atoms. (C) 2001 Elsevier Science BN. All rights reserved.

Half-sandwich metal diselenolate complexes Cp#M(NO)(SePh)(2) (M = Mo or W; Cp# = Cp or MeCp) as ligands. Synthesis of selenolate-bridged heterobimetallic compounds

The reactions of half-sandwich diselenolate Mo and W complexes (CpM)-M-#(NO)(SePh)(2) (M = Mo; Cp-# = Cp' (1a), MeCp (1b); M = W; Cp-# = Cp' (1c)) with (Norb)Mo(CO)(4), Ni(COD)(2) and Fe(CO)(5) have been investigated. Treatment of (1a), (1b) and (1c) with (Norb)Mo(CO)(4) in PhMe gave the bimetallic complexes: Cp'Mo(NO)(mu -SePh)(2)Mo(CO)(4) (2a), MeCpMo(NO)(mu -SePh)(2)Mo(CO)(4) (2b) and Cp'W(NO)(mu -SePh)(2)Mo(CO)(4) (2c) in moderate yields. Irradiation of (1a) and (1c) in the presence of Fe(CO)(5) gave heterobimetallic complexes Cp'Mo(CO)(mu -SePh)(2)Fe(CO)(3) (3a) and Cp'W(NO)(mu -SePh)(2)Fe(CO)(3) (3c). Ni(COD)(2) reacts with two equivalents of (1a), (1b) and (1c) to give [Cp'Mo(NO)(mu -SePh)(2)](2)Ni (4a), [MeCpMo(NO)(mu -SePh)(2)](2)Ni (4b) and [Cp'W(NO)(mu -SePh)(2)](2)Ni (4c) in good yields. The new heterobimetallic complexes were characterized by i.r., H-1-n.m.r., C-13-n.m.r. and EI-MS spectroscopy.

Half-sandwich cyclopentandienyl molybdenum and tungsten nitrosyl complexes containing bidentate sulfur ligands

Half-sandwich nitrosyl complexes Cp*M(NO)I-2 (M = Mo, or W) react with dithiocarbamates (NaS2CNMe2 and NaS2CNEt2) in THF to form of complexes: Cp*Mo(NO)I (S2CNMe2) (1), Cp*Mo(NO)I(S2CNEt2) (2), Cp*W(NO)I(S2CNMe2) (3) and Cp*W(NO)I(S2CNEt2) (4) in high yields. Treatments of Cp*M(NO)I-2 (M = Mo, W) or [CpMo(NO)I-2](2) with phosphinodithioate (NaS2PMe2) and phosphorodithioate [(NH4)S2P(OMe)(2)] result in complexes: Cp*Mo(NO)I(S2PMe2) (5a), CpMo(NO)I (S2PMe2) (5b), Cp*Mo(NO)(S2PMe2)(2) (6a), CpMo (NO) (S2PMe2)(2) (6b) and Cp*Mo(NO)I[S2P(OMe)(2)] (7), Cp*W(NO)I(S2PMe2) (8), Cp*W(NO) I[S2P(OMe)](2) (9). Treatment of (5a) and (5b) with an excess of NaS2PMe2 gives (6a) and (6b). The complexes have been characterized by their elemental analyses, i.r., H-1, C-13-n.m.r. and by EI-MS spectrometry.

The use of half-sandwich iridium dithiolate and diselenolate complexes, Cp*Ir(L)(ER)(2) (L = CO, PMe3, PPh3; ER = SPh, SePh, SeMe), for the synthesis of heterodimetallic compounds. The molecular structure of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)]

Carbonyl-iridium half-sandwich compounds, Cp*Ir(CO)(EPh)(2) (E = S, Se), were prepared by the photo-induced reaction of Cp*Ir(CO)(2) with the diphenyl dichalcogenides, E2Ph2, and used as neutral chelating ligands in carbonylmetal complexes such as Cp*Ir(CO)(mu-EPh)(2)[Cr(CO)(4)], Cp*Ir(CO)(mu-EPh)(2)[Mo(CO)(4)] and Cp*Ir(CO)(mu-EPh)(2)[Fe(CO)(3)], respectively. A trimethylphosphane - iridium analogue, Cp*Ir(PMe3)(mu-SeMe)(2)[Cr(CO)(4)], was also obtained. The new heterodimetallic complexes were characterized by IR and NMR spectroscopy, and the molecular geometry of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)] has been determined by a single crystal X-ray structure analysis. According to the long Ir...Mo distance (395.3(1) Angstrom), direct metal-metal interactions appear to be absent. (C) 1998 Elsevier Science S.A. All rights reserved.

STRUCTURE-PROPERTY RELATIONSHIP BETWEEN HALF-WAVE POTENTIALS OF ORGANIC-COMPOUNDS AND THEIR TOPOLOGY

A significant correlation was found between half-wave potentials of organic compounds and their topological indices, A(x1), A(x2), and A(x3). The simplicity of calculation of the index from the connectivity in the molecular skeleton, together with the significant correlation, indicates its practical value. Good results have been obtained by using them to predict the half-wave potentials of some organic compounds.

PREPARATION AND STRUCTURE OF HALF-OPEN VANADOCENE, V[2,4-(CH3)2C5H5](C5H5)CO

The half-open vanadocene, V[2,4-(CH3)2C5H5](C5H5)CO, was obtained by the reaction of V[2,4-(CH3)2C5H5](C5H5)PMe3 with CO in petroleum ether at room temperature. Its crystal structure was determined by X-ray diffraction technique. The crystal was monoclinic with space group P2(1)/n, a = 16.614(3), b = 7.636(1), c = 19.128(6) angstrom, beta = 99.92(2)-degrees, V = 2390.5(9) angstrom3, and Z = 8. The final R value was 0.043. The V(1)-CPD(1) (half) (PD = 2,4-(CH3)2C5H5) bonds were shorter (0.038 angstrom) than the V(1)-CCP(1) (half) (CP = C5H5) bonds, averaging 2.224(4) versus 2.262(4) angstrom, respectively. 4V[2,4-(CH3)2C5H5](C5H5)CO has been characterized by IR and EPR methods.

地震P-S波时差耦合作用的斜坡崩滑效应研究

China locates between the circum-Pacific and the Mediterranean-Himalayan seismic belt. The seismic activities in our country are very frequent and so are the collapses and slides of slope triggered by earthquakes. Many collapses and slides of slope take place mainly in the west of China with many earthquakes and mountains, especially in Sichuan and Yunnan Provinces. When a strong earthquake happening, the damage especially in mountains area caused by geological hazards it triggered such as rock collapses, landslides and debris flows is heavier than that it caused directly. A conclusion which the number of lives lost caused by geological hazards triggered by a strong earthquake in mountains area often accounts for a half even more of the total one induced by the strong earthquake can be made by consulting the statistical loss of several representative earthquakes. As a result, geological hazards such as collapses and slides of slope triggered by strong earthquakes attract wide attention for their great costs. Based on field geological investigation, engineering geological exploration and material data analysis, chief conclusions have been drawn after systematic research on formation mechanism, key inducing factors, dynamic characteristics of geological hazards such as collapses and slides of slope triggered by strong earthquakes by means of engineering geomechanics comprehensive analysis, finite difference numerical simulation test, in-lab dynamic triaxial shear test of rock, discrete element numerical simulation. Based on research on a great number of collapses and landslides triggered by Wenchuan and Xiaonanhai Earthquake, two-set methods, i.e. the method for original topography recovering based on factors such as lithology and elevation comparing and the method for reconstructing collapsing and sliding process of slope based on characteristics of seism tectonic zone, structural fissure, diameter spatial distribution of slope debris mass, propagation direction and mechanical property of seismic wave, have been gotten. What is more, types, formation mechanism and dynamic characteristics of collapses and slides of slope induced by strong earthquakes are discussed comprehensively. Firstly, collapsed and slided accumulative mass is in a state of heavily even more broken. Secondly, dynamic process of slope collapsing and sliding consists of almost four stages, i.e. broken, thrown, crushed and river blocked. Thirdly, classified according to failure forms, there are usually four types which are made up of collapsing, land sliding, land sliding-debris flowing and vibrating liquefaction. Finally, as for key inducing factors in slope collapsing and sliding, they often include characteristics of seism tectonic belts, structure and construction of rock mass, terrain and physiognomy, weathering degree of rock mass and mechanical functions of seismic waves. Based on microscopic study on initial fracturing of slope caused by seismic effect, combined with two change trends which include ratio of vertical vs. horizontal peak ground acceleration corresponding to epicentral distance and enlarging effect of peak ground acceleration along slope, key inducing factor of initial slope fracturing in various area with different epicentral distance is obtained. In near-field area, i.e. epicentral distance being less than 30 km, tensile strength of rock mass is a key intrinsic factor inducing initial fracturing of slope undergoing seismic effect whereas shear strength of rock mass is the one when epicentral distance is more than 30 km. In the latter circumstance, research by means of finite difference numerical simulation test and in-lab dynamic triaxial shear test of rock shows that initial fracture begins always in the place of slope shoulder. The fact that fracture strain and shear strength which are proportional to buried depth of rock mass in the place of slope shoulder are less than other place and peak ground acceleration is enlarged in the place causes prior failure at slope shoulder. Key extrinsic factors inducing dynamic fracture of slope at different distances to epicenter have been obtained through discrete element numerical simulation on the total process of collapsing and sliding of slope triggered by Wenchuan Earthquake. Research shows that combined action of P and S seismic waves is the key factor inducing collapsing and sliding of slope at a distance less than 64 km to initial epicenter along earthquake-triggering structure. What is more, vertical tensile action of P seismic wave plays a leading role near epicenter, whereas vertical shear action of S seismic wave plays a leading role gradually with epicentral distance increasing in this range. On the other hand, single action of P seismic wave becomes the key factor inducing collapsing and sliding of slope at a distance between 64 km and 216 km to initial epicenter. Horizontal tensile action of P seismic wave becomes the key factor gradually from combined action between vertical and horizontal tensile action of P seismic wave with epicentral distance increasing in this distance range. In addition, initial failure triggered by strong earthquakes begins almost in the place of slope shoulder. However, initial failure beginning from toe of slope relates probably with gradient and rock occurrence. Finally, starting time of initial failure in slope increases usually with epicentral distance. It is perhaps that the starting time increasing is a result of attenuating of seismic wave from epicenter along earthquake-triggering structure. It is of great theoretical and practical significance for us to construct towns and infrastructure in fragile geological environment along seism tectonic belts and conduct risk management on earthquake-triggered geological hazards by referring to above conclusions.