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71.
Arno Behr 《Angewandte Chemie (International ed. in English)》1988,27(5):661-678
The carbon dioxide molecule has been of limited importance as a synthetic unit in organic chemistry. When it is coordinated to transition metals, however, completely new possibilities arise; CO2 can bond to metal complexes in a variety of ways and can enter into insertion and coupling reactions, or become catalytically attached to other substrates. The formation of C? C bonds between carbon dioxide and unsaturated hydrocarbons under conditions of homogeneous catalysis makes available new synthetic routes to industrially interesting organic compounds. 相似文献
72.
A density functional theory investigation on a series of sandwich-type transition metal complexes [(CBO)n]2M (n=4–6; M=transition metals) with carbon boronyls (CBO)n as effective aromatic ligands has been presented in this work at B3LYP level. The ground-states of these complexes possess staggered Dnd symmetries, while the corresponding eclipsed Dnh structures exist as transition states with slightly higher energies (within 5.8 kJ/mol). Carbon boronyl complexes [(CBO)n]2M are confirmed to be much more stable than their boron carbonyl isomers [(BCO)n]2M, which, on the other hand, take eclipsed ground-states with Dnh symmetries. The carbon boronyl complexes [(BCO)n]2M proposed in this work parallelize the well-known sandwich-type hydrocarbon complexes [CnHn]2M in coordination chemistry with boronyl groups –BO isolobal to –H atoms in corresponding ligands. 相似文献
73.
Matthias Bauer Christoph Gastl Christoph Köppl Guido Kickelbick Helmut Bertagnolli 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):567-581
Summary. The molecular structure of the transition metal alkoxide Zr(OnBu)4 in toluene and its modification by addition of i-propanol, tetrahydrofurane, and the coordinating ligand pentane-1,3-dione (Hacac) were investigated by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy.
Zr(OnBu)4 dissolved in toluene forms dimers. It was proved that cluster size is a function of the number of added equivalents ligand.
In contrast, the addition of i-propanol or tetrahydrofurane caused no structural changes observable by EXAFS spectroscopy. A detailed discussion of the
structural models is given in terms of possible alternatives and errors within the EXAFS analysis. 相似文献
74.
The systematic integration of the small 2π- and 4π-electron systems cyclopropenylium ion, cyclopropenone, oxo-cyclobutenylium ion, and cyclobutadiene into phane chemistry was initiated only a few years ago. [n2]Cyclopropenylophanes, [n2]cyclopropenonophanes, metal-capped [n4]cyclobutadienosuperphanes, and other new families of double-decker phane species became available from cycloalkydiynes through special methods of double [2+1]cycloaddition with carbenes and metal complex induced dimerization by double [2+2]cycloaddition. Phane-specific structural features were elucidated by X-ray structural analyses. Cyclic voltammetry and PE spectroscopy as well as MO calculations reealed considerable interactions between closely spaced π-electron systems. Decapping cyclobutadienosuperphanes formally extended the synthetic principle to threefold [2+2]cycloadditions resulting in [n4]-bridged tricyclo-[4.2.0.03, 5]octa-3,7-dienes, which represent a new type of cage compounds. Moreover, completion to fourfold [2+2]addition was achieved with the photoinduced transformation of [34]bridged tricyclo[4.2.0.03, 5]octa-3,7-diene into propella[34]cubane. 相似文献
75.
Static pressure usually increases the transition temperatures of polymers by decreasing their free volume. If the pressurizing medium is soluble in the polymer matrix, the opposing effect of increasing the free volume is possible. Those shifts of transition temperatures were monitored with a medium-pressure Differential Scanning Calorimetry (DSC) device. The influences of sorbed and surrounding gas molecules are demonstrated by changes occurring in the transition temperature regions. The results show the severe plasticizing effect of CO2 on poly(p-phenylene sulphide) (PPS). The glass transition temperature TG and the temperature of crystallization TC are influenced by sorbed gas molecules. They decrease due to sorbed CO2 molecules. Glass transition is lowered, but is difficult to interpret, as relaxation phenomena which diminish with increasing pressure occur during DSC runs. In crystallites no gas solution is usually possible, so that the melting point of PPS is mainly affected by influences other than plasticization. 相似文献
76.
Antonio Fernández-Ramos Benjamin A. Ellingson Rubén Meana-Pañeda Jorge M. C. Marques Donald G. Truhlar 《Theoretical chemistry accounts》2007,118(4):813-826
This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them
to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational
symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i)
if the reaction is symmetric, (ii) if reactants and/or transition states are chiral, (iii) if the reaction has multiple conformers
for reactants and/or transition states and, (iv) if there is an internal rotation of part of the molecular system. All these
four situations are treated systematically and analyzed in detail in the present article. We also include a large number of
examples to clarify some complicated situations, and in the last section we discuss an example involving an achiral diasteroisomer. 相似文献
77.
Nek M. Shaikh S. Hafeez M.A. Baig 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1311-1320
We report the measurement of the zinc and cadmium plasma parameters produced by the fundamental, second, and third harmonics of the neodymium-doped yttrium aluminium garnet laser. The excitation temperature has been determined from the Boltzmann plot method, whereas the electron number density is estimated from the Stark broadened profile of several spectral lines. The temporal evolution of the plasma has also been investigated. Besides, we present experimental relative transition probabilities of the Zn (4s5s 3S1 → 4s4p 3P0,1,2) and Cd (5s6s 3S1 → 5s5p 3P0,1,2) triplets and compare our data with that listed in the National Institute of Standards and Technology database. The experiments have been performed in air but also in He, Ne and Ar atmosphere to study the effects of ambient gas environment on the emission intensity of the atomic and ionic lines and on the plasma parameters. 相似文献
78.
Jacques Barrau Ghassoub Rima Tajani El Amraoui 《Journal of organometallic chemistry》1998,570(2):8645
The reactions of the divalent species (ArO)2M (Ar=2,4,6-[(CH3)2NCH2]3C6H2; M=Ge, Sn) with either Me3SiN3, elemental S8, Se or transition metal complexes M′(CO)n+1 (M′=Fe, n=4; M′=Cr, W; n=5) (Ph3P)2Pt·C2H4 have resulted in the isolation of either the new stable formal metallanimines (ArO)2M=N–SiMe3, germanethione, -selone (ArO)2Ge=E (E=S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)2M=M′(CO)n, (ArO)2M=Pt(PPh3)2 complexes, respectively. The direct oxidation of the (ArO)2M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)2M–O–]2. All of the chalcogenido- and transition metal–metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)2Ge=E (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)2M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione. 相似文献
79.
80.
Daniel Canseco-González 《Journal of organometallic chemistry》2003,679(1):101-109
The complexes cis-[M(Ph2PC6H4-2-S)2] M=Ni, Pd, Pt were stereoselectively synthesized by transmetallation reactions of [M(Cl)2(NCC6H5)2] M=Pd, Pt or NiCl2·6H2O with [Sn(R)2(Ph2PC6H4-2-S)2] R=Ph, nBu or tBu. The conformation of the Pd and Pt derivatives being unequivocally confirmed by single crystal X-ray diffraction studies showing both metal centers to be into a slightly distorted square planar environment, the main distortion being due to the steric hindrance caused by the aromatic rings in the phosphine moiety. 相似文献