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Daura-Oller E Segarra AM Poblet JM Claver C Fernández E Bo C 《The Journal of organic chemistry》2004,69(8):2669-2680
We studied the hydroboration of vinylarenes using rhodium complexes bearing atropoisomeric ligands. For the first time, an NMR spectroscopy study of the styrene and catecholborane addition to the precursor of catalyst [Rh(COD)(L-L)]BF(4), where L-L = (R)-BINAP and (R)-QUINAP, showed evidence of the structure of intermediates involved in the catalytic cycle. On the basis of this evidence, and using DFT calculations and QM/MM strategies, we investigated the origin of regio- and stereoselectivity. We determined the structure and stability of the key intermediates for several ligands and substrates and found excellent agreement between the relative stability of the intermediates and the experimentally observed trends. Using model systems, we analyzed the role of the steric and electronic features of the ligands and the substrates in detail. 相似文献
154.
155.
Error growth in the numerical integration of periodic orbits by multistep methods, with application to reversible systems 总被引:4,自引:0,他引:4
We study the growth with time of (the coefficients of the asymptoticexpansion of) the error in the numerical integration with linearmultistep methods of periodic solutions of systems of ordinarydifferential equations. Particular attention is devoted to reversiblesystems. It turns out that symmetric linear multistep methodscannot be recommended in spite of the fact that they mimic thereversibility of the true flow. For reversible second-ordersystems, linear multistep methods without parasitic double rootsare useful. 相似文献
156.
We describe a simple method to measure the top quark mass in the
channel that may be useful in Run II of D? detector. The method is validated by applying it to the Run Ib eμ data. 相似文献
157.
JM Chatterjee M Saha Sarkar S Bhattacharya P Banerjee S Sarkar RP Singh S Murulithar RK Bhowmik 《Pramana》2001,57(1):165-169
High-spin states of 95,97Mo (Z=42, N=53,55) nuclei have been investigated through 82Se(18O, xn) reaction at Eb=60 MeV. The level scheme in 95Mo has been observed upto ≏ 10 MeV in the present experiment. The level structure shows mainly single particle character.
In 97Mo, the ground state level sequence has been extended to ≏ 4.5 MeV while the previous information had been up to 2.4 MeV.
A negative parity band built on 1437 keV (11/2−) excited state has been extended to 5.5 MeV. The structure seems to show a coexistence of single particle and collective
modes of excitation. Properties of both the nuclei have been compared with shell model calculations using OXBASH. 相似文献
158.
Background
Clinical spinal cord injury in domestic dogs provides a model population in which to test the efficacy of putative therapeutic interventions for human spinal cord injury. To achieve this potential a robust method of functional analysis is required so that statistical comparison of numerical data derived from treated and control animals can be achieved. 相似文献159.
160.
Mercado BQ Chen N Rodríguez-Fortea A Mackey MA Stevenson S Echegoyen L Poblet JM Olmstead MM Balch AL 《Journal of the American Chemical Society》2011,133(17):6752-6760
Single-crystal X-ray diffraction studies of Sc(2)(μ(2)-S)@C(s)(6)-C(82)·Ni(II)(OEP)·2C(6)H(6) and Sc(2)(μ(2)-S)@C(3v)(8)-C(82)·Ni(II)(OEP)·2C(6)H(6) reveal that both contain fully ordered fullerene cages. The crystallographic data for Sc(2)(μ(2)-S)@C(s)(6)-C(82)·Ni(II)(OEP)·2C(6)H(6) show two remarkable features: the presence of two slightly different cage sites and a fully ordered molecule Sc(2)(μ(2)-S)@C(s)(6)-C(82) in one of these sites. The Sc-S-Sc angles in Sc(2)(μ(2)-S)@C(s)(6)-C(82) (113.84(3)°) and Sc(2)(μ(2)-S)@C(3v)(8)-C(82) differ (97.34(13)°). This is the first case where the nature and structure of the fullerene cage isomer exerts a demonstrable effect on the geometry of the cluster contained within. Computational studies have shown that, among the nine isomers that follow the isolated pentagon rule for C(82), the cage stability changes markedly between 0 and 250 K, but the C(s)(6)-C(82) cage is preferred at temperatures ≥250 °C when using the energies obtained with the free encapsulated model (FEM). However, the C(3v)(8)-C(82) cage is preferred at temperatures ≥250 °C using the energies obtained by rigid rotor-harmonic oscillator (RRHO) approximation. These results corroborate the fact that both cages are observed and likely to trap the Sc(2)(μ(2)-S) cluster, whereas earlier FEM and RRHO calculations predicted only the C(s)(6)-C(82) cage is likely to trap the Sc(2)(μ(2)-O) cluster. We also compare the recently published electrochemistry of the sulfide-containing Sc(2)(μ(2)-S)@C(s)(6)-C(82) to that of corresponding oxide-containing Sc(2)(μ(2)-O)@C(s)(6)-C(82). 相似文献