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61.
Walter K. Dean Gary L. Simon Paul M. Treichel Lawrence F. Dahl 《Journal of organometallic chemistry》1973,50(1):193-207
The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2, has been accomplished by the reaction of NaMn(CO)5 with (CH3)3SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C6H5)3 bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C6H5)3 bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor. 相似文献
62.
Infrared fluorescence observed after exciting to ν6 (ν=1) of CD3H with a Q-switched CO2 laser yields the exponential deactivation rate constant of 0.84 ms?1 torr?1. Rate constants for deactivation of CD3H by rare gases vary from 1.4 (for He) to 0.029 (for Xe) ms?1 torr?1. 相似文献
63.
The MNDO scheme has been reparametrized for hydrocarbons using both molecular binding energies and heats of formation at 0 K as experimental reference data. Compared with MNDO, there are only minor changes in the optimized parameters, and the results are essentially of the same accuracy. These tests justify the use of heats of formation at 298 K as reference data in the original MNDO parametrization. 相似文献
64.
Walter Lund 《Fresenius' Journal of Analytical Chemistry》1990,337(5):557-564
Summary The different aspects of speciation analysis are reviewed. Species-specific instrumental techniques as well as various speciation schemes are considered for the determination of species of metals and metalloids, including organometallic compounds. The application of the methods are discussed in some detail for the analysis of natural waters, air, soil, sediment and biological samples. The relationship between metal species and bioavailability is also briefly dealt with. 相似文献
65.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
66.
Kuno Wagner Kurt Findeisen Walter Schfer Werner Dietrich 《Angewandte Chemie (International ed. in English)》1981,20(10):819-830
Research in the field of low-molecular weight, oligomeric and polymeric α,ω-diisocyanatocarbodiimides and -polycarbodiimides has been fruitful, not only in connection with these compounds themselves, but also—as so often happens in chemistry—with quite different problems. Novel synthetic methods, discoveries concerning the properties of low-molecular weight carbodiimides and phosphane imide derivatives, as well as results on the fragmentation reactions of four-membered heterocyclic compounds containing oxygen, phosphorus, and nitrogen, and a better understanding of the diisocyanate polyaddition process are among the many by-products of this research. The “high- and low-temperature formation” of polycarbodiimides and the homogeneous and heterogeneous catalysis of this process are described, and the fundamental importance of four-membered ring fragmentation mechanisms resulting in the formation of phosphane imide derivatives is outlined. Interesting building blocks for the diisocyanate polyaddition and polycondensation processes can be synthesized by many derivatization reactions of oligomeric and high-molecular weight polycarbodiimides and polyuretonimines. The in situ production of polycarbodiimides via matrix reactions in flexible polyurethane foams leads to a cellular arrangement of the material due to the pronounced symmetrical growth processes. Combination-foams with increased carbonation tendencies are formed in this way. Attention is drawn to several industrial applications of α,ω-diisocyanatopolycarbodiimides, of high-molecular weight cross-linked polyuretonimines, and of polycarbodiimide foams. 相似文献
67.
Kaspar Hegetschweiler Isidor Erni Walter Schneider Helmut Schmalle 《Helvetica chimica acta》1990,73(1):97-105
1,3,5-Trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (TDCI) and 1,3,5-trideoxy-1,3,5-tris(trimethylammonio)-cis-inositol (TTCI) were prepared by methylation of 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (TACI). The ability of TDCI to form both intermolecular and intramolecular H-bonds, as demonstrated by X-ray diffraction, is probably responsible for the good solubility of TDCI in almost every common solvent. TTCI was found to be a polyol of unusual high acidity (pK1 = 8.14 ± 0.02, pK2 = 13.0 ± 0.2). This phenomenon could be explained by electrostatic interactions between the charged substituents of the cyclohexane residue. 相似文献
68.
William Heilman Ernst Kupfer Walter Keller-Schierlein Hans Zhner Heinz Wolf Heinrich H. Peter 《Helvetica chimica acta》1979,62(1):1-6
From cultures of the Avilamycin (Avilamycin A) producing organism, Streptomyces viridochromogenes, strain ETH 23575, a second antibiotic, Avilamycin C, C61H90Cl2O32 could be isolated in crystalline form. Both Avilamycins belong to the group of the Orthosomycins. By IR., 1H- and 13C-NMR. spectroscopy and by transformation to a common derivative it could be proven that Avilamycin A is a methyl ketone, Avilamycin C the corresponding methyl carbinol. 相似文献
69.
The ion-pair generation rate (ionization topography) in plasmas from63Ni and particularly Ti3H4 foils, as used in electron capture detectors, was measured at room temperature using large, parallel plates of low backscattering ability in nitrogen gas of varying density. For one atmosphere pressure, the fall-off of ion pair formation as calculated from the exponential region equalsN
0·e
–0.19d
for63Ni andN
0·e
–1.4d
for3H (whereN
0 is the initial ionization rate immediately adjacent to the foil andd is the distance from the foil in mm). The experimentally measured half ranges (distances from the foil within which 50% of all possible ion pairs are created) are 2.7 mm for63Ni and 0.27 mm for3H. The half ranges calculated from the exponential region where there is less interference from electron backscattering, are 3.7 and 0.5 mm, respectively. The latter values are considered closer to the true, unimpeded ionization topography near planar63Ni and3H foils.Material taken from doctoral thesis 相似文献
70.