Metallacycloalkanes: I. Preparation and characterisation of α,α′-bipyridyl-5-nickela-3,3,7,7-tetramethyl-trans-tricyclo[4.1.0.02,4]heptane

Oxidative addition of 2 molecules of 3,3-dimethylcyclopropene (I) to α,α′-bipyridyl(1,5-cyclooctadiene)nickel(0) (III) gave the title compound (IV) in over 90% yield. Complex IV was characterized by mass, ¹H NMR and ¹³C NMR spectroscopy. Its structure was determined by X-ray diffraction (a 13.7081(2), b 14.638(2), c 9.5139(1) Å, β 110.82(1)°, C2/c, R = 0.05 for 1614 reflections).     

低温加氢催化剂的设计: 理论与实践

简要总结了我们在C=C及C=O双键低温加氢双金属催化剂方面的最新研究成果. 首先, 我们以环己烯加氢为探针反应, 证明了平行使用多种研究手段的重要性, 包括单晶表面的基础研究与DFT计算, 多晶表面的合成与表征, 负载型催化剂的制备与性能测试等. 其次, 总结了双金属催化剂在其他加氢反应, 如丙烯醛C=O双键的选择性加氢, 苯的低温加氢, 以及乙炔的选择性加氢等反应中的应用. 最后, 讨论了利用金属碳化物代替贵金属Pt以减少双金属催化剂中Pt用量的可能性.     

Unexpected open-chain molecular structure of a titanocenyl-substituted dimethyl ether

Reaction of (η-C₅H₄CH₃)₂TiCl₂ with CH₃OCH₂MgCl yielded (η-C₅H₄-CH₃)₂Ti(Cl)CH₂OCH₃ (2a). Complex 2a crystallizes in space group P2₁/n with cell constants a 8.162(1), b 11.004(2), c 15.297(2) Å, β 96.40(1)°. In contrast to the three-membered metallacyclic zirconium compound of analogous composition (η-C₅H₅)₂Zr(Cl)CH₂OCH₃ (1), the titanocenyl-substituted ether 2a has an open-chain (η¹-O“-outside”) type structure.     

Optical rotatory dispersion studies—CIV Low-temperature circular dichroism behavior of various chromophoric derivatives of alcohols and amines

The low-temperature circular dichroism behavior of various cyclic and alicyclic systems containing the methyl xanthato-, N,N-diethyl-N′-acylthioureyl-, N-phthalimido-, nitrito- and dithio-carbalkoxy- chromophores is discussed. Rotational strength (R₀^T) values are reported where possible and changes in this parameter upon variation of the temperature are interpreted, where relevant, in terms of the degree of steric inhibition to free rotation about the various bonds connected to the asymmetric center bearing (or nearest to) the chromophore moiety.     

Macrolide antibiotics—VIII The absolute configuration of certain centers in neomethymycin, erythromycin and related antibiotics

Neomethymycin (I) has been transformed into “anhydrocycloneomethynolide” (V) which could be degraded via (−)--methyllevulinic acid to (−)--methylsuccinic acid, thus establishing the absolute configuration of positions 4 and 6 in the lactonic acid (XIII). This acid is a common degradation product of methymycin, neomethymycin, pikromycin and narbomycin and there is thus available a standard of absolute configuration for these macrolide antibiotics. By a different sequence of reactions, erythromycin (XXIII) has been converted into (+)--methyllevulinic acid and (+)--methylsuccinic acid. Coupled with earlier results reported in the literature, it is now possible to assign absolute configurations to positions 10 (R) and 8 (R) of erythromycin and this applies most likely also to positions 4 (R) and 2 (S). Attention is called to the biogenetic significance of these observations.     

The heats of reaction of phosphines and phosphites with toluene-molybdenum tricarbonyl. Importance of both steric and electronic factors in determining the Mo---PR3 bond strength

The heats of reaction of tolueneMo(CO)₃ with a series of phosphines and phosphites have been measured by solution calorimetry. The order of stability toward formation of fac-(PR₃)₃Mo(CO)₃ in THF solution is: P(OCH₃)₃s> PMe₃ > PⁿBu₃ > PMe₂Ph> PEt₃ > triphos> P(OPh)₃ > PMePh₂ > PPh₃ > PCl₃ and spans a range of 25 kcal/mol reflecting individual bond strength differences up to 8 kcal/mol. The bulky phosphines PCy₃ and P^tBu₃ react with tolueneMo(CO)₃ in THF, but 30–40 kcal/mol less heat is evolved in these reactions than with the other phosphines and phosphites. The coordinately unsaturated five-coordinate complexes (PR₃)₂Mo(CO)₃ are proposed as the reaction products. The importance of both steric and electronic factors in the Mo---P bond is discussed.     

Synthesis and first molecular structure of a bis-2-spiro-1-boraadamantane derivative

[reaction: see text] A new method for synthesizing the 2-spiro-boraadamantane pyridine complex (2) from 1-ethynylcyclohexylmethyl ether has been developed. The chemistry has been applied to the synthesis of bis-2-spiro-1-boraadamantane.pyridine (1) from trans-1,4-diethynyl-1,4-dimethoxycyclohexane (8). This bis-Lewis acid serves as a self-assembling molecular building block with difunctional Lewis bases.     

Conformational changes of pyrene-labeled polyelectrolytes with pH: effect of hydrophobic modifications

Structural changes of pyrene-labeled and unlabeled poly(maleic acid/octyl vinyl ether) (PMAOVE) and poly(maleic acid/methyl vinyl ether) (PMAMVE) with changes in pH have been investigated in this study. The changes in the photophysical properties of pyrene are interpreted to investigate uncoiling or swelling of the polymeric chains with pH. The vibrational fine structure of the pyrene fluorescence (I(3)/I(1)) and the ratio between excimer and monomer fluorescence (I(e)/I(m)) of both pyrene-labeled and unlabeled PMAMVE and PMAOVE suggest that, at pH 4, the polymers are in the coiled form and PMAOVE forms hydrophobic nanodomains. An increase in pH ionizes a number of COOH groups on both PMAMVE and PMAOVE, which leads to the stretching or swelling of the polymers.     

A new thermoelectric material: CsBi4Te6

The highly anisotropic material CsBi(4)Te(6) was prepared by the reaction of Cs/Bi(2)Te(3) around 600 degrees C. The compound crystallizes in the monoclinic space group C2/m with a = 51.9205(8) A, b = 4.4025(1) A, c = 14.5118(3) A, beta = 101.480(1) degrees, V = 3250.75(11) A(3), and Z = 8. The final R values are R(1) = 0.0585 and wR(2) = 0.1127 for all data. The compound has a 2-D structure composed of NaCl-type [Bi(4)Te(6)] anionic layers and Cs(+) ions residing between the layers. The [Bi(4)Te(6)] layers are interconnected by Bi-Bi bonds at a distance of 3.2383(10) A. This material is a narrow gap semiconductor. Optimization studies on the thermoelectric properties with a variety of doping agents show that the electrical properties of CsBi(4)Te(6) can be tuned to yield an optimized thermoelectric material which is promising for low-temperature applications. SbI(3) doping resulted in p-type behavior and a maximum power factor of 51.5 microW/cm.K(2) at 184 K and the corresponding ZT of 0.82 at 225 K. The highest power factor of 59.8 microW/cm.K(2) at 151 K was obtained from 0.06% Sb-doped material. We report here the synthesis, physicochemical properties, doping characteristics, charge-transport properties, and thermal conductivity. Also presented are studies on n-type CsBi(4)Te(6) and comparisons to those of p-type.