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71.
Paul A. Keifer Donald L. Nagel Norman H. Cromwell 《Journal of heterocyclic chemistry》1988,25(2):353-359
A series of ten N-alkyl(aralkyl)-2-phenyl-3-cyanoaziridines has been synthesized to continue investigations of the molecular stereochemistry and bonding of functionalized aziridines. Substantial spectroscopic evidence is presented which indicates the presence of stereoselective hyperconjugation between the phenyl and nitrile groups and the aziridine ring. The 1H and 13C nmr chemical shifts are rationalized in terms of the interactions of the substituents on the aziridine ring, and how these interactions vary with the steric bulk of the nitrogen substituents. Various stereoselective coupling constants (1H-1H and 13C-1H) are also reported. 相似文献
72.
Fuentes-Cabrera M Nicholson DM Sumpter BG Widom M 《The Journal of chemical physics》2005,123(12):124713
We investigate the possibility of tailoring the electronic properties of isoreticular metal-organic materials by replacing the metal atom in the metal-organic cluster and by doping. The electronic structure of M-IRMOF1, where IRMOF1 stands for isoreticular metal-organic framework 1 and M = Be, Mg, Ca, Zn, and Cd, was examined using density-functional theory. The results show that these materials have similar band gaps (ca. 3.5 eV) and a conduction band that is split into two bands, the lower of which has a width that varies with metal substitution. This variation prompted us to investigate whether doping with Al or Li could be used to tailor the electronic properties of the Zn-IRMOF1 and Be-IRMOF1 materials. It is shown that replacing one metal atom with Al can effectively be used to create IRMOFs with different metallic properties. On the other hand, adding Li produces structural changes that render this approach less suitable. 相似文献
73.
Kim C. Pich Roger Bishop Donald C. Craig Ian G. Dance A. David Rae Marcia L. Scudder 《Structural chemistry》1993,4(1):41-51
In a further exploration of the structural factors causing alicyclic diols such asexo-2,exo-6-dihydroxy-2,6-dimethylbicyclo[3.3.1]nonane (1) to adopt the helical tubuland inclusion host structure, the title compound (8) has been synthesized and its crystal structure determined. This 9-oxa analogue of (1) has a totally different structure [C10H18O3; orthorhombic;P21212;a 18.989(4),b 19.064(3),c 14.256(3) Å;Z 20; with finalR 0.065] due to involvement of the ether oxygen atom in the hydrogen bonding network. The structure of the diol (8) approximatesP¯421
c symmetry, and 16 of the 20 molecules per cell create a hostlike structure of this symmetry, which consists of tightly bound hydrogen bonded pillars parallel toc. The remaining guestlike molecules occupy inequivalent pseudo ¯4 sites separated byc/2 to form weakly bound columns parallel toc. Hydrogen bonds also occur between the pillars and columns. An ordered structure with sensible intermolecular contacts can be formed inP212121 with thec axis doubled. A difference betweena andb axial lengths correlates with a difference in occupancies of pseudo-¯4-related sites for the guest-like component of the structure. 相似文献
74.
M. Scott Goodman Margaret A. Goodman Andrey Y. Kovalevsky Alexander Y. Nazarenko Donald Pope 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(2):m30-m32
The title copper(II) complex, [Cu(C22H18N6)2](ClO4)2·2C2H3N, comprises two neutral substituted tris(pyrazol‐1‐yl)methane ligands bonded to a central CuII ion, which is positioned on a crystallographic inversion center. Six Cu—N bonds are arranged in a distorted octahedral fashion. The unsubstituted pyrazole rings on each ligand are oriented trans with respect to each other, interdigitated with the two 3‐phenylpyrazole rings of the other ligand. 相似文献
75.
Alison T. Ung Roger Bishop Donald C. Craig Ian G. Dance A. David Rae Marcia L. Scudder 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(4):385-398
The inclusion compounds of 2,8-dimethyltricyclo[5.3.1.13,9]dodecane-syn-2,syn-8-diol,3, with ferrocene and with squalene have been prepared. The crystal structures of these helical tubulate compounds: (3)3·(ferrocene)0.75 [P3121,a=b=13.7480(6),c=7.0312(5) Å,Z=1,R=0.038] and (3)3·(squalene)0.23 [P3121,a=b=13.677(1),c=7.0533(9) Å,Z=1,R=0.042] are described.
Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82151 (16 pages). 相似文献
76.
de Namor AF Chahine S Castellano EE Piro OE Jenkins HD 《Chemical communications (Cambridge, England)》2005,(30):3844-3846
An additive thermodynamic contribution of pendant arms to the complexation of calixarene derivatives with mercury(II) in acetonitrile is for the first time demonstrated. 相似文献
77.
Adelfinskaya O Nashine VC Bergstrom DE Davisson VJ 《Journal of the American Chemical Society》2005,127(46):16000-16001
Two oxadiazole carboxamide deoxyribonucleoside analogues are described that can be incorporated and efficiently extended by Taq DNA polymerase. The primer strand extension beyond oxadiazole nucleoside analogues occurs at rates similar to the values observed for the canonical Watson-Crick base pairs irrespective of the template nucleobase. These distinctive chemical effects in DNA polymerase extensions are attributed to the smaller size and unique electronic properties of the oxadiazole nucleobase. 相似文献
78.
From relative integrated intensity measurements of the symmetric stretching vibration of nitrate ion in nitric acid solutions (both HNO
3
/H
2
O and DNO
3
/D
2
O), the mass law concentration quotients, Q
were obtained as functions of concentration. By extrapolation the limiting dissociation constants were estimated to be 24.4 and 15 respectively at 25°C. It is shown that this constant refers to a process in which the ion pair H
3
O+ NO
3
–
is in equilibrium with the dispersed, solvated H
3
O+ and NO
3
–
ions. 相似文献
79.
Time-resolved measurements of the thermal lens effect have been made for CH3F, CH3CI and C2H4. This technique is compared to others used in the study of vibrational relaxation phenomena and is found to be applicable to the study of a wide variety of gaseous systems at relatively low pressures. Translational cooling has been observed in CH3F and an approximate lower limit of 200 msec-1 has been established for the rate of this cooling process, which corresponds to equilibration of the ν3 and ν6 states, in a mixture of 0.2 torr CH3F and 10 torr Ar. 相似文献
80.
We show that the Ashtekar-Isham extension
of the configuration space of Yang-Mills theories
is (topologically and measure-theoretically) the projective limit of a family of finite dimensional spaces associated with arbitrary finite lattices.These results are then used to prove that
is contained in a zero measure subset of
with respect to the diffeomorphism invariant Ashtekar-Lewandowski measure on
. Much as in scalar field theory, this implies that states in the quantum theory associated with this measure can be realized as functions on the extended configuration space
. 相似文献