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Schott D Sleigh CJ Lowe JP Duckett SB Mawby RJ Partridge MG 《Inorganic chemistry》2002,41(11):2960-2970
NMR studies reveal that complexes Ru(CO)(2)(H)(2)L(2) (L = PMe(3), PMe(2)Ph, and AsMe(2)Ph) can have three geometries, ccc, cct-L, and cct-CO, with equilibrium ratios that are highly dependent on the electronic properties of L; the cct-L form is favored, because the sigma-only hydride donor is located trans to CO rather than L. When L = PMe(3), the ccc form is only visible when p-H(2) is used to amplify its spectral features. In contrast, when L = AsMe(2)Ph, the ccc and cct-L forms are present in similar quantities and, hence, must have similar free energies; for this complex, however, the cct-CO isomer is also detectable. These complexes undergo a number of dynamic processes. For L(2) = dppe, an interchange of the hydride positions within the ccc form is shown to be accompanied by synchronized CO exchange and interchange of the two phosphorus atoms. This process is believed to involve the formation of a trigonal bipyramidal transition state containing an eta(2)-H(2) ligand; in view of the fact that k(HH)/k(DD) is 1.04 and the synchronized rotation when L(2) = dppe, this transition state must contain little H-H bonding character. Pathways leading to isomer interconversion are suggested to involve related structures containing eta(2)-H(2) ligands. The inverse kinetic isotope effect, k(HH)/k(DD) = 0.5, observed for the reductive elimination of dihydrogen from Ru(CO)(2)(H)(2)dppe suggests that substantial H-H bond formation occurs before the H(2) is actually released from the complex. Evidence for a substantial steric influence on the entropy of activation explains why Ru(CO)(2)(H)(2)dppe undergoes the most rapid hydride exchange. Our studies also indicate that the species [Ru(CO)(2)L(2)], involved in the addition of H(2) to form Ru(CO)(2)(H)(2)L(2), must have singlet electron configurations. 相似文献
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Methylolation and condensation products formed in caprolactam-formaldehyde reaction mixtures have been identified using nuclear magnetic resonance (NMR) and mass spectrometry (MS). Previously unreported side-products were also detected. All of the reaction products were separated by micellar electrokinetic chromatography (MEKC) and high performance liquid chromatography (HPLC), and the separation parameters, such as efficiency and distribution constants, obtained in the two techniques were compared. For quantification, the response factors for the monomers were determined using standard calibration and hydrolysis, whilst those for the condensation products were deduced from the values of the monomers. The accurate determination of the response factors was confirmed by checking the mass balance of a known mixture. 相似文献
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Newly observed data on the rotational constants of carbon su?ide in excited vibrational states of the low-wavenumber bending vibration ν7 have been successfully interpreted in terms of the two-dimensional anharmonic oscillator wavefunctions associated with this vibration. By combining these results with published infrared and Raman spectra the vibrational assignment has been extended and a refined bending potential for ν7 has been derived: this has a minimum at a bending angle of about 24° at the central C atom, with an energy maximum at the linear configuration some 23 cm?1 above the minimum. From similar data on the combination and hot bands of ν7 with ν4 (1587 cm?1) and ν2 (786 cm?1) the effective ν7 bending potential has also been determined in the one-quantum excited states of ν4 and ν2. The effective ν7 potential shows significant changes from the ground vibrational state; the central hump in the ν7 potential surface is increased to about 50 cm?1 in the v4 = 1 state, and decreased to about 1 cm?1 in the v2 = 1 state. In the light of these results vibrational assignments are suggested for most of the observed bands in the infrared and Raman spectra of C3O2. 相似文献
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Godard C Duckett SB Parsons S Perutz RN 《Chemical communications (Cambridge, England)》2003,(18):2332-2333
UV irradiation of a solution of (eta5-C5H5)bis(ethene)rhodium in the presence of 2,2'-dipyridylketone yields (eta5-C5H5)Rh(kappa2-N,O-2,2'-dipyridylketone) which inserts ethene to yield a bicyclic oxametallacyclopentane. 相似文献
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Overtone spectrum of o, m and p-nitrobenzaldehydes and p-chlorobenzaldehyde has been studied in 2000–12000 cm−1 region. Vibrational frequencies and anharmonicity constants for aryl as well as alkyl CH stretch vibrations have been determined.
We have also determined the internuclear distances for the aryl CH bond in the different molecules. The small variation observed
in these distances is an indication of the substitution effect.
It is observed that in the case of p-disubstituted benzens, the shift in aryl CH bond is proportional to sum of the Hammet σ of the substituents. However in the
case of o-disubstituted benzenes it is only 80% of the para-substituted shift. 相似文献
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The study of reactions by NMR spectroscopy is normally limited by the poor detection limits offered by the method. An overview is presented of how chemical reactions can be studied using parahydrogen-assisted NMR spectroscopy, where detected signals can have strengths that exceed those normally available by factors that approach 31,000. 相似文献
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