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11.
Hölscher M Leitner W Holthausen MC Frenking G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4700-4708
Quantum chemical calculations by using density functional theory at the B3LYP level have been carried out to elucidate the reaction course for the addition of ethylene to [OsO2(CH2)2] (1). The calculations predict that the kinetically most favorable reaction proceeds with an activation barrier of 8.1 kcal mol(-1) via [3+2] addition across the O=Os=CH2 moiety. This reaction is -42.4 kcal mol(-1) exothermic. Alternatively, the [3+2] addition to the H2C=Os=CH2 fragment of 1 leads to the most stable addition product 4 (-72.7 kcal mol(-1)), yet this process has a higher activation barrier (13.0 kcal mol(-1)). The [3+2] addition to the O=Os=O fragment yielding 2 is kinetically (27.5 kcal mol(-1)) and thermodynamically (-7.0 kcal mol(-1)) the least favorable [3+2] reaction. The formal [2+2] addition to the Os=O and Os=CH2 double bonds proceeds by initial rearrangement of 1 to the metallaoxirane 1 a. The rearrangement 1-->1 a and the following [2+2] additions have significantly higher activation barriers (>30 kcal mol(-1)) than the [3+2] reactions. Another isomer of 1 is the dioxoosmacyclopropane 1 b, which is 56.2 kcal mol(-1) lower in energy than 1. The activation barrier for the 1-->1 b isomerization is 15.7 kcal mol(-1). The calculations predict that there are no energetically favorable addition reactions of ethylene with 1 b. The isomeric form 1 c containing a peroxo group is too high in energy to be relevant for the reaction course. The accuracy of the B3LYP results is corroborated by high level post-HF CCSD(T) calculations for a subset of species. 相似文献
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Jacob RE Laicher G Minard KR 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,188(2):357-366
In (3)He magnetic resonance images of pulmonary air spaces, the confining architecture of the parenchymal tissue results in a non-Gaussian distribution of signal phase that non-exponentially attenuates image intensity as diffusion weighting is increased. Here, two approaches previously used for the analysis of non-Gaussian effects in the lung are compared and related using diffusion-weighted (3)He MR images of mechanically ventilated rats. One approach is model-based and was presented by Yablonskiy et al., while the other approach utilizes the second order decay contribution that is predicted from the cumulant expansion theorem. Total lung coverage is achieved using a hybrid 3D pulse sequence that combines conventional phase encoding with sparse radial sampling for efficient gas usage. This enables the acquisition of nine 3D images using a total of only approximately 1 L of hyperpolarized (3)He gas. Diffusion weighting ranges from 0 s/cm(2) to 40 s/cm(2). Results show that the non-Gaussian effects of (3)He gas diffusion in healthy rat lungs are directly attributed to the anisotropic geometry of lung microstructure as predicted by the Yablonskiy model, and that quantitative analysis over the entire lung can be reliably repeated in time-course studies of the same animal. 相似文献
16.
Guohai Deng Dr. Sudip Pan Dr. Jiaye Jin Prof. Dr. Guanjun Wang Prof. Lili Zhao Prof. Dr. Mingfei Zhou Prof. Gernot Frenking 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):412-418
Two structural isomers containing five second-row element atoms with 24 valence electrons were generated and identified by matrix-isolation IR spectroscopy and quantum chemical calculations. The OCBNO complex, which is produced by the reaction of boron atoms with mixtures of carbon monoxide and nitric oxide in solid neon, rearranges to the more stable OBNCO isomer on UV excitation. Bonding analysis indicates that the OCBNO complex is best described by the bonding interactions between a triplet-state boron cation with an electron configuration of (2s)0(2pσ)0(2pπ)2 and the CO/NO− ligands in the triplet state forming two degenerate electron-sharing π bonds and two ligand-to-boron dative σ bonds. 相似文献
17.
Alexander S. Ivanov Prof. Dr. Alexander I. Boldyrev Prof. Dr. Gernot Frenking 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(9):2431-2435
A theoretical study of Li90P90, which possesses a circular double‐helix structure that resembles the Watson–Crick DNA structure, is reported. This is a new bonding motif in inorganic chemistry. The calculations show that the molecule might become synthesized and that it could be a model for other inorganic species which possess a double‐helix structure. 相似文献
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Ekkehard Fluck Manfred Spahn Gernot Heckmann Horst Borrmann Axel Obermeyer 《Heteroatom Chemistry》1991,2(5):593-599
1,1,3,3 - Tetrakis(dimethylamino) - 1λ5,3λ5 - diphosphete, 1 , reacts with cyanoformic acid methyl ester to form two isomers of the title compound 2 . Properties, NMR, mass, and IR spectra of 2 , as well as the molecular and crystal structure of the E isomer of 2 , are described and discussed. 相似文献
20.
Let R be a discrete nonsingular equivalence relation on a standard probability space , and let V be an ergodic strongly asymptotically central automorphism of R. We prove that every V-invariant cocycle with values in a Polish group G takes values in an abelian subgroup of G.
The hypotheses of this result are satisfied, for example, if A is a finite set, a closed, shift-invariant subset, V is the shift, μ a shift-invariant and ergodic probability measure on X, the two-sided tail-equivalence relation on X, a shift-invariant subrelation which is μ-nonsingular, and a shift-invariant cocycle. 相似文献