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31.
The theory of chirality functions described in a previous publication is generalized to allow for chiral ligands. In the earlier theory, all symmetry operations of the molecular frame could be thought of as permutations of the ligands among the sites; in the present work, improper rotations not only permute the ligands, but convert them into mirror images. The group that generates all isomers from a given ordered molecule belonging to a frame with n sites is now the hyperoctahedral group of order 2n
n! consisting of all possible combinations of permutations and site reflections. The representation theory of these groups is described, and applied to the problem of constructing qualitatively complete chirality functions, and of deciding which ligand partitions, and which isomer mixtures, are chiral. It is found useful to classify chiral representations of the covering group as ligand specific and class specific. The ligand specific representations describe chiral properties which are common to all frames and arise purely from the chirality of the ligands, while the class specific representations describe the chiral properties of the frame. A number of examples are explicitly worked out. 相似文献
32.
The enthalpy change of the reaction at 298 K between Br2 (l) and Sn(c) in CS2 as solvent giving SnBr4 (s) has been determined by calorimetry to be (?374, 2±1.4) kJ·mol?1, [(?89.45±0.33) kcal·mol?1]. By the same method the heat of solution of SnBr4 (c) in CS2 has been found to be (11.9±0.3) kJ·mol?1, [(2.84±0.08) kcal·mol?1]. Combining these results, a value of (?386.1±1.5) kJ·mol?1, [(?92.3±0.4) kcal·mol?1] is derived for the standard heat of formation of SnBr4 (c). Substituting this figure in the thermochemical cycle hitherto used for calculating the heat of formation of SnBr4 (c) gives ?124.3 kcal·mol?1 for the standard heat of formation of SnCl4 (l), which is in reasonable agreement with a recent determination of this quantity8. 相似文献
33.
34.
Zusammenfassung Darstellung und Eigenschaften von Ammonium-, Kalium-, Silber- und Thalliumsalzen des Triselenimides und der Diimidotriselensäure werden beschrieben, Infrarot-Spektren sowieDebye-Scherrer-Diagramme einiger dieser erstmalig dargestellten Verbindungen werden zu ihrer Charakterisierung mitgeteilt.Mit 3 Abbildungen1. Mitt.:A. Engelbrecht undF. Clementi, Mh. Chem.92, 555 (1961). 相似文献
35.
Alfred Trautwein Yutaka Maeda Frank E. Harris Helmuth Formanek 《Theoretical chemistry accounts》1974,36(1):67-76
Experimental Mössbauer spectra of the Fe57-enriched CO complex of sperm whale myoglobin (MbCO) at T= 4.2 K with and without applied magnetic field (H⊥γ) were measured to derive the sign of the electric field gradient (EFG), the quadrupole splitting ΔE Q, and the isomer shift δ of the heme iron. We find a positive EFG, δE Q = 0.363 mm/sec, and δ + 0.266 mm/sec. Molecular orbital calculations were carried out to obtain theoretical estimates of EFG and ΔE Q for several steric arrangements of the CO ligand relative to the heme group. Our results are most consistent with the conclusion that the iron is situated in the heme plane, and that a bent geometry with a Fe-C-O angle of about 135 ° is more favorable than a more symmetric structure with a linear Fe-C-O geometry. 相似文献
36.
Zusammenfassung Beim Abbau von Paucin wird Brenzcatechin, Kaffeesäure und Putrescin erhalten. Daraus und aus spektroskopischen Befunden ergibt sich für das Paucin die Strukturformel3.
Mit 6 Abbildungen
Meinem Lehrer, Prof. Dr.H. Bretschneider, zum 65. Geburtstag gewidmet. 相似文献
The structure of Paucine
Paucine can be degradated to catechol, caffeic acid and putrescine. This together with spectroscopic data allows us to deduce formula3 for paucine.
Mit 6 Abbildungen
Meinem Lehrer, Prof. Dr.H. Bretschneider, zum 65. Geburtstag gewidmet. 相似文献
37.
38.
Ntaoleng M. Makunya Reinout Meijboom Alfred Muller 《Journal of organometallic chemistry》2005,690(18):4159-4167
Cyclopentadienyldicarbonylmethyliron, [CpFe(CO)2Me] (1), undergoes migratory carbonyl insertion under the influence of isosteric phosphine ligands P(4-FC6H4)3 and P(4-MeC6H4)3. The products of the reaction, [CpFe(CO)(COMe)P(4-FC6H4)3] (2a) and [CpFe(CO)(COMe)P(4-MeC6H4)3] (2b), were characterised by X-ray crystallography. In both structures, the iron atom adopts a pseudo octahedral coordination geometry. Fe-P bond distances are the same at 2.1932(8) Å in 2a and 2b, respectively. Thus, contrary to what was expected, X-ray data could not be used to quantitatively differentiate between the two phosphine ligands in 2a and 2b. Therefore, additional spectroscopic techniques such as IR and NMR were employed. Similarly, the Fe-C bond lengths of the carbonyl (Fe-CO) and acetyl (Fe-COMe) are 1.748(3) and 1.955(3) in 2a, and 1.744(3) and 1.951(3) Å in 2b, respectively.The migratory carbonyl insertion was studied by NMR, IR, and UV-vis spectroscopies to determine the mechanism and the rate law. Results from NMR spectroscopy show that the formation of the product is accompanied by oxidation of the corresponding phosphine ligand. An increase in the reactivity of migratory carbonyl insertion for P(4-MeC6H4)3 was observed when the solvent was changed from CH2Cl2 to MeCN. The kinetic data showed that P(4-MeC6H4)3 reacts faster than P(4-FC6H4)3. 相似文献
39.
Synthese of sulfonated derivatives of 2-amino-p-xylene Sulfonation of 2-amino-p-xylene (2) gave 2-amino-p-xylene-5-sulfonic acid (1) . The 2-amino-p-xylene-6-sulfonic acid (3) was prepared via three routes: (1) sulfonation of 2-amino-5-chloro-p-xylene (19) to 5-amino-2-chloro-p-xylene-3-sulfonic acid (20) followed by hydrogenolysis; (2) sulfur dioxide treatment of the diazonium salt derived from 2-amino-6-nitro-p-xylene (21) to 2-nitro-p-xylene-6-sulfonyl chloride (11) followed by hydrolysis to 2-nitro-p-xylene-6-sulfonic acid (4) and Béchamp reduction; (3) Béchamp reduction of 2-chloro-3-nitro-p-xylene-5-sulfonic acid (13) to 3-amino-2-chloro-p-xylene-5-sulfonic acid (16) and subsequent hydrogenolysis. Catalytic reduction of 13 in aqueous sodium carbonate solution gave mixtures of 3 and 16 . 2-Amino-p-xylene-3-sulfonic acid (27) was synthesized via two routes: (1) reaction of 19 with sulfamic acid to 2-amino-5-chloro-p-xylene-3-sulfonic acid (26) followed by hydrogenolysis; (2) sulfur dioxide treatment of the diazonium salt derived from 2-amino-3-nitro-p-xylene (28) to 2-nitro-p-xylene-3-sulfonyl chloride (12) , hydrolysis to 2-nitro-p-xylene-3-sulfonic acid (7) and Béchamp reduction. 相似文献