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71.
Gareth R. Lewis Alexander J. Blake 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m398-m400
The title complex, [NiCl(C12H16N3O2)2(H2O)]NO3·2CH4O·H2O, was obtained from a methanolic solution of Ni(NO3)2·6H2O, 2‐pyridyl nitronyl nitroxide (2‐NITpy) and (NEt4)2[CoCl4]. The equatorial coordination sites of the octahedral NiII centre are occupied by two chelating radical ligands, with the axial positions occupied by the Cl? and water ligands. The H2O—Ni—Cl axis of the complex lies along a crystallographic twofold axis, so that only half the cation is present in the asymmetric unit. The Ni—Cl bond length [2.3614 (17) Å] is significantly shorter than distances typical of octahedral NiII centres [2.441 (5) Å]. However, with only one nitrate anion per formula unit, the oxidation state of the metal must be assigned as NiII. The 2‐NITpy ligands bend away from the equatorial plane, forming a hydrophobic region around the Cl atoms. Conversely, the ligated water molecule forms moderately strong hydrogen bonds with the disordered methanol solvent molecules, which in turn form interactions with the water of crystallization and the disordered nitrate anion. These interactions combine to give hydrophilic regions throughout the crystal structure. 相似文献
72.
Angelo J. Amoroso Brian F. G. Johnson Jack Lewis Chi-Keung Li Catherine A. Morewood Paul R. Raithby Maria D. Vargas Wing-Tak Wong 《Journal of Cluster Science》1995,6(1):163-173
Reduction of the heptaosmium cluster [Os7(CO)21] With [Et4N][NH4) gives the cluster dianion [Os7(CO)20]2–,1, in high yield. The reaction of the dianion with [AuPR
3Cl] (R=Et or Ph) in the presence of TlPF6 forms [Os7((CO)20(AuPR
3)2] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C6H6)(CH3CN)3]2+ gives [Os8(CO)20 (
6-C6H6)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph4P]+ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt3 groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C6H6) unit capped to a triangular face, to give a bicapped octahedral framework. 相似文献
73.
74.
Lewis CM 《Physical review D: Particles and fields》1991,44(6):1661-1669
75.
Armstrong TA Bettoni D Bharadwaj V Biino C Borreani G Broemmelsiek D Buzzo A Calabrese R Ceccucci A Cester R Church M Dalpiaz P Dalpiaz PF Dibenedetto R Dimitroyannis D Fabbri MG Fast J Gianoli A Ginsburg CM Gollwitzer K Hahn A Hasan M Hsueh S Lewis R Luppi E Macrí M Majewska AM Mandelkern M Marchetto F Marinelli M Marques J Marsh W Martini M Masuzawa M Menichetti E Migliori A Mussa R Palestini S Pallavicini M Pastrone N Patrignani C Peoples J Pesando L Petrucci F Pia MG Pordes S Rapidis P 《Physical review letters》1992,69(16):2337-2340
76.
Lewis K. Panell Henry M. Fales John P. Scovill Daniel L. Klayman Douglas X. West Ramon L. Tate 《Transition Metal Chemistry》1985,10(4):141-147
Summary Californium-252 plasma desorption mass spectra were recorded for complexes of the anions of various thio-and seleno-semicarbazones of 3-acetylpyridines(1–4) with the transition metal ions iron(III) and cobalt(II). Positive ion spectra gave clear evidence of the cation present and fragmentation with loss of ligands or parts of ligands was straightforward. Negative ion spectra likewise provided evidence of the intact anion except with tetracoordinate metal halide systems [MX4]– which lost one or more halide atoms. Evidence of fragmentation of the ligand and recombination of the fragments with the metal ion was also observed in the negative ion mode. Spectra were used to revise the structure of a complex previously reported as [FeLCl2](1) to [FeL2]+[FeCl4]–. 相似文献
77.
Dipole-moment derivatives, calculated by both the CNDO/2 method with different parameterizations and the INDO method, are compared to the experimental values determined from absolute infrared intensity measurements for the IR active modes of methane, ethane, ethylene and acetylene. A parameter refinement procedure is introduced in which the CNDO/2 molecular orbital parameters are adjusted through a damped least-squares treatment to give best agreement with the observed dipole-moment derivatives. It is found that the refinement does not substantially improve the agreement obtained with the original CNDO/2 parameterization. The INDO method gives somewhat poorer agreement than the CNDO/2 calculations. As an example of the applicability of the molecular orbital methods toward reproducing relative infrared intensities, the spectrum of cyclopropane in the gasphase is examined.
Zusammenfassung Die Ableitungen des Dipol-Moments, die nach der CNDO/2-Methode mit verschiedenen Parametrisierungen sowie der INDO-Methode berechnet wurden, werden mit den experimentellen Ergebnissen aus Messungen der absoluten Infrarot-Intensitäten für die IR-aktiven Schwingungen von Methan, Äthan, Äthylen und Azetylen verglichen. Die CNDO/2-Parameter werden mit einer Methode der kleinsten Quadrate den beobachteten Dipol-Moment-Ableitungen angepaßt. Die Ergebnisse sind jedoch nicht wesentlich von denen der ursprünglichen CNDO/2-Methode verschieden. Die INDO-Ergebnisse sind nicht so gut wie die CNDO/2-Ergebnisse. Als Beispiel der Anwendbarkeit der MO-Methoden zur Berechnung von relativen IR-Intensitäten wird das Spektrum des Cyclopropans in der Gasphase untersucht.
Résumé Les dérivées du moment dipolaire, calculées par la méthode CNDO/2 avec différentes paramétrisations et par la méthode INDO, sont comparées aux valeurs expérimentales déterminées à partir de mesures d'intensité absolue pour les modes actifs dans l'infra-rouge dans le méthane, l'éthane, l'éthylène et l'acétylène. Les paramètres sont ajustés de manière à donner le meilleur accord avec les dérivées du moment dipolaire. Cet ajustement n'améliore pas sensiblement l'accord obtenu avec la paramétrisation CNDO/2 originale. La méthode INDO donne des résultats moins bons que les calculs CNDO/2. Le spectre du cyclopropane en phase gazeuse est étudié comme exemple de l'applicabilité de la méthode des orbitales moléculaires au calcul des intensités relatives infra-rouge.相似文献
78.
Badham NF Mendelson WL Allen A Diederich AM Eggleston DS Filan JJ Freyer AJ Killmer LB Kowalski CJ Liu L Novack VJ Vogt FG Webb KS Yang J 《The Journal of organic chemistry》2002,67(15):5440-5443
A convenient two-step homologation of both aliphatic and aromatic ketones to the corresponding carboxylic acid has been developed. First ketones were converted to epoxynitriles with the Darzens reaction. Second, a Lewis acid mediated rearrangement of these epoxynitriles with lithium bromide was achieved to give homologated secondary alkanoic acids (as well as aryl-alkanoic) in good yields. The mechanism and the scope of the rearrangement reaction were investigated. This strategy constitutes a two-step homologation of ketones to secondary carboxylic acids. 相似文献
79.
Millet O Muhandiram DR Skrynnikov NR Kay LE 《Journal of the American Chemical Society》2002,124(22):6439-6448
New pulse sequences are presented for the measurement of the relaxation of deuterium double quantum, quadrupolar order, and transverse antiphase magnetization in (13)CH(2)D methyl groups of (15)N-, (13)C-labeled, fractionally deuterated proteins. Together with previously developed experiments for measuring deuterium longitudinal and transverse decay rates [Muhandiram, D. R.; Yamazaki, T.; Sykes, B. D.; Kay, L. E. J. Am. Chem. Soc. 1995, 117, 11536], these schemes allow measurement of the five unique decay constants of a single deuteron, providing an unprecedented opportunity to investigate side-chain dynamics in proteins. All five deuterium relaxation rates have been measured for deuterons in the methyl groups of the B1 immunoglobulin binding domain of peptostreptococcal protein L and the N-terminal SH3 domain from the protein drk. Since values of the spectral density function at only three different frequencies contribute to the five relaxation rates, the self-consistency of the relaxation data is readily established. Very good agreement is obtained between calculated parameters describing the amplitudes and time scales of motion when different subsets of the relaxation data are employed. 相似文献
80.
Lewis BR Gibson ST Zhang W Lefebvre-Brion H Robbe JM 《The Journal of chemical physics》2005,122(14):144302
Separate coupled-channel Schr?dinger-equation (CSE) models of the interacting (1)Pi(u) (b,c,o) and (3)Pi(u) (C,C(')) states of N(2) are combined, through the inclusion of spin-orbit interactions, to produce a five-channel CSE model of the N(2) predissociation. Comparison of the model calculations with an experimental database, consisting principally of detailed new measurements of the vibrational and isotopic dependence of the (1)Pi(u) linewidths and lifetimes, provides convincing evidence that the predissociation of the lowest (1)Pi(u) levels in N(2) is primarily an indirect process, involving spin-orbit coupling between the b (1)Pi(u)- and C (3)Pi(u)-state levels, the latter levels themselves heavily predissociated electrostatically by the C(') (3)Pi(u) continuum. The well-known large width of the b(v=3) level in (14)N(2) is caused by an accidental degeneracy with C(v=9). This CSE model provides the first quantitative explanation of the predissociation mechanism for the dipole-accessible (1)Pi(u) states of N(2), and is thus likely to prove useful in the construction of realistic radiative-transfer and photochemical models for nitrogen-rich planetary atmospheres. 相似文献