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81.
Some cationic five coordinate complexes of formula [Os(CO)(NO)L2A]PF6 (L = tertiary phosphine, A = an acetylene) have been prepared by reaction of the appropriate acetylene with [Os(CO)(NO)L2(acetone)]PF6; the variable temperature 1H NMR spectra of some of these indicate that the coordinated π-acetylene undergoes fluxional behaviour. 相似文献
82.
Twenty-two aromatic amines are determined by the diazotization-coupling spectrophotometric technique, using 8-amino-1-hydroxynaphthalene-3,6-disulphonic acid (H-acid) and N-(1-naphthyl) ethylenediamine (N-na) as coupling agents. The following are determined by both methods: 2-and 4-ethylaniline, 4-aminobenzonitrile, 3- and 4-aminoacetophenone, 4-aminobenzophenone, 4-iodoaniline, 2,5-dichloroaniline, 4-aminohippuric acid, 2-aminobenzyl alcohol, 3-aminobenzamide, sulphathiazole, 2-, 3- and 4-methoxyaniline and 2,4-, 3,4- and 3,5-dimethylaniline. It is possible to determine 2,3- and 2,5-dimethylaniline only by the H-acid method, but 2,6-dimethylaniline cannot be determined by either method. 2-Aminobenzamide can only be determined by the N-na method. In the application of the H-acid method to the methoxyanilines and dimethylanilines, the colour is developed by adding a large excess of sodium bicarbonate and H-acid. In the application of the N-na method to the ethylanilines, methoxyanilines and 2,4-, 3,4- and 3,5-dimethylanilines, the colour is developed by addition of a large excess of N-na reagent and allowing the solution to stand overnight. 相似文献
83.
R.S. Sapienza P.E. Riley R.E. Davis R. Pettit 《Journal of organometallic chemistry》1976,121(2):C35-C40
A general synthesis for the preparation of medium sized cycloalkanes having 1,2-butadienyl substituents is described. The reaction sequence involved acylation of butadiene-iron tricarbonyl with a diacid chloride, reduction of the resultant diketone to a diol derivative and conversion with HBF4 to an acyclic bis-pentadienyl Fe(C0)3 dicationic complex. Upon treatment with zinc the dication undergoes intramolecular ring closure to afford the bis-Fe(C0)3 complex of the 1,2-dibutadienyl cycloalkane. Five-, six- and ten-membered cyclolalkene derivatives have been prepared in this manner. 相似文献
84.
W. Richter 《Accreditation and quality assurance》1997,2(8):354-359
Primary methods of measurement have a central function in metrology. They are an essential component in the realisation of
the SI units and therefore are indispensable for establishing traceability of measurements of all kinds of physical quantities
to the corresponding SI units. This is also true for chemical analysis. Gravimetry, titrimetry, coulometry, and isotope dilution
mass spectrometry (IDMS) are evaluated with regard to their potential to be primary methods according to a general definition
of primary methods recently given by the Comité Consultatif pour la Quantité de Matière (CCQM). Optical absorption spectrometry
and methods based on colligative properties are also considered. A general scheme for establishing traceability of chemical
measurements to the SI units using primary methods is discussed.
Received: 17 April 1997 · Accepted: 9 August 1997 相似文献
85.
86.
Mössbauer studies are reported for compounds of the type KMIIMIIIF6 (M = first-row transition metal ion, Zn, or Mg) which have the tetragonal bronze structure. The results of this investigation provide evidence that the trivalent ions are located on the 8(j) sites of the bronze structure and that the divalent ions are distributed over both the 8(j) and 2(c) sites. 相似文献
87.
(±) - 33,7 - Trimethyl - 2,9 - dioxatricyclo[3.3.1.04,7]nonane 1 and (±) - 3,3,7 - trimethyl - 2,9-dioxatricyclo [4.2.1.04,7]nonane 2 were synthesized. The former was shown to be (±)-lineatin, an ambrosia beetle pheromone. A selective synthesis of (±)-lineatin was devised, which was modified to yield the both enantiomers of lineatin via optical resolution of an intermediate. 相似文献
88.
Dean C. Luehrs Richard E. Brown Kalpana A. Godbole 《Journal of solution chemistry》1989,18(5):463-469
A linear free energy relationship was found betweenv
max, the energy of the absorption maximum of chloride, bromide, or iodide ion in various solvents, and the solvatochromic parameter which is a measure of the hydrogen bond donor ability of the solvent. The relationships are: for chloride,v
max=6.99+50.16 kK; for bromide,v
max=5.52+45.20 kK; for iodide,v
max=5.02+40.33 kK. The correlation ofv
max for iodide ion with gave a larger correlation coefficient and smaller standard deviation than a correlation with the E
T
(30) parameter of Dimroth. From the values ofv
max for iodide ion and the solvated electron in liquid ammonia at 25°C, these correlations indicate a preliminary value of 0.00 for the parameter of liquid ammonia. This had not been reported before and is lower than expected from a general knowledge of the physical and chemical properties of liquid ammonia but is consistent with a more detailed consideration and recent gas phase measurements of hydrogen bond donor strength. 相似文献
89.
Boris A. Trofimov Ol’ga V. Petrova Lyubov’ N. Sobenina Igor’ A. Ushakov Al’bina I. Mikhaleva Yurii Yu. Rusakov Leonid B. Krivdin 《Tetrahedron letters》2006,47(22):3645-3648
Functionalized pyrrolic enols, 2-(2,2-dicyano-1-hydroxyethenyl)-1-methylpyrroles, synthesized from 2-ethenylpyrroles by a nucleophilic SEt-OH exchange, upon heating (75-142 °C) are readily rearranged to their 3-isomers in near to quantitative yield. The inter or intramolecular auto-protonation of a pyrrole ring by the acidic enol hydroxyl to form a mesomeric pyrrolium cation or zwitterion is suggested to be a key step in the rearrangement. 相似文献
90.
Lorraine P. McDonnell Bushnell Eric R. Evitt Robert G. Bergman 《Journal of organometallic chemistry》1978,157(4):445-456
Reactions of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)2-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes. 相似文献