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81.
The successive reaction of (CO)6M with Na[NCR21] and [Et3O]BF4 yields (CO)5M[C(NCR21)OEt] (II: M = Cr; III: M = W; CR21 = C(C6H4Br-p)2 (a), CPh2 (b), C(C6H4OMe-p)2 (c), C(C6H4)2O (d), CBu2tt (e)). Hexacarbonyltungsten, (CO)6W, reacts with Na[NCPh2] and MeOSO2F to give (CO)5W[C(NCPh2) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me3),C,N,C(Me3) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes.  相似文献   
82.
Single crystals of CaPdF4 (purple) and CdPdF4 (dark blue) have been obtained by heating CaF2 (CdF2) with PdF2 at 820°C (900°C) for ca. 20–30 d in sealed Pd (Pt) tubes. CaPdF4 crystallizes tetragonal (KBrF4-Type) with a = 5.521, c = 10.570 Å (space group I4/mcm ? D184h, No. 140) Z = 4, 283 unique reflexions, R = 0.083; Rw = 0.079, CdPdF4 cubic (CaF2-variant) with a = 5.403 Å (space group Pa3 ? T6h, No. 205) Z = 4, 165 unique reflexions, R = 0.047, Rw = 0.032. The high pressure modification of PdF2, obtained by heating PdF2 in closed Pt-tubes under a pressure of ≈ 60 kbar and ‘HgPdF4’, both black, a = 5.327 Å and a = 5.43 Å are isotypic. CaPdF4 is diamagnetic, CdPdF4 and HPPdF2 are antiferromegnetic.  相似文献   
83.
Syntheses of New N-Vinylpyrroles The reactions of pyrrolyl potassium ( 1 ) with (ethoxymethylene)malonic acid derivatives 2a–e yielded the carbanions 3a–e , which could be hydrolyzed to 4a–e , but with the exception of 4b they were not isolated, because a transformation to the N-vinylpyrroles 5a , c–e by elimination of ethanol took place; 1 reacted with 2b at 80°C to give 4b and 6 . Hydrolysis of 4b with KOH yielded 4g , which eliminated 1 mol of ethanol to form 5f , decarboxylation of which led to N-vinylpyrrole 7 . By cyclization of 5e under various conditions the pyrrolizines 8a , b are obtained, the hydrolysis of which did not give ketone 9 but only amino alcohol 10 . Some other cyclizations of 11a–c and 13 yielded the 3H-pyrrolizine derivatives 12a–c and 14 , respectively.  相似文献   
84.
The free NH3 molecule and the [Zn(NH3)4]2+ ion were studied by the kinematic coupling approach. The pure effects of this coupling were found to be small, and some modifications had to be introduced in order to get a reasonable force field. The force constants deduced for the skeletal vibrations are comparable with those of a quasi-exact force field. Calculated frequencies for [68Zn(NH3)4]2+ and [64Zn(ND3)4]2+ are reported in addition to those of [64Zn(NH3)4]2+. Mean amplitudes of vibration for [64Zn(NH3)4]2+ are given.  相似文献   
85.
The basic obstacles for the general use of laser-ablation(LA)-ICP-MS in analytical laboratories are connected with its reproducibility and calibration. A mathematical relation deduced from the correlation function of the analytical signals allows the estimation of the number of craters needed for representative analyses. The procedure was applied to different samples such as manganese crusts and soils. The ion intensities of the major elements in the manganese crusts and nodules were used as internal standards, improving relative standard deviations by factors between 2 and 3. Selected samples of wood and manganese crusts were analyzed by LA-ICP-MS and the results compared with those obtained by solution ICP-MS. The agreement of the values is within the 95% confidence limits. Powdered reference materials and, in the case of wood analysis, cellulose doped with standard solutions were used for the calibration.  相似文献   
86.
N.M.R. Investigation of Methylphosphonium Chloride The n.m.r. spectra of [CH3PH3]Cl in aqueous hydrochloric acid as solvent and of [OP(CH3) (OCH2CH2Cl)OCH2? ]2 in C6D6 und CD2Cl2 are described. 31P n.m.r. resonances with a line width at half height of 55 Hz are found for the H2O? HCl solutions of [CH3PH3]Cl in the solid state at 183 K.  相似文献   
87.
The photoelectron(PE)spectrum of tricyclo[3.1.0.02,6] hex-2-ene(benzvalene 1) has been recorded. The first four bands in the PE spectrum of 1 can be assigned to transitions to 2B2, 2A1, 2A2 and 2B1 states of 11. This assignment is discussed in terms of the results of semiempirical and ab initio calculations on 1. Furthermore the highest occupied MO's of 1 are derived qualitatively from an interaction diagram between a distorted bicyclobutane and an ethylene moiety.  相似文献   
88.
A systematic study of activation analysis with cyclotron-produced neutrons for (n, 2n), (n, p) and (n, α) reactions is presented. The limits of detection for elements of atomic number from 6 to 80 are given. The possibilities of optimization of irradiation conditions by the choice of the most suitable neutron spectrum are discussed. The potential of this fast neutron activation analysis method is compared with that of 14 MeV neutron activation analysis.  相似文献   
89.
The 4-pyrazoline-3-one1 reacts with 4-dimethylaminobenzaldehyde to yield the stable asymmetric cyanine dye2b which reacts with1 to give the colorless (aryl) (dipyrazolyl) methane3b. Using aldehydes with less cationstabilizing groups the polymethines2 are not isolated but only the methanes3. The structures of2b and3 are discussed by1 H,13C and Hetero NMR spectra.  相似文献   
90.
Zusammenfassung Die Infrarot-und Raman-Spektren folgender Hydroxylamin-Derivate wurden registriert und zugeordnet: (CH3)3SiONH2 (1), (CH3)3SiONHSi(CH3)3, (CH3)3SiON[Si(CH3)3]2 (3), CH3ONH2 (4), CH3ON[Si(CH3)3]2 (5), CH3NHOCH3, CH3N[Si(CH3)3]OCH3, (C2H5)2NOH und (C2H5)2NOSi(CH3)3. Eine Normalkoordinatenanalyse für NH2OH,1, 3, 4 und5 zeigt, daß sich die Spektren durch Übertragung gleichbleibender Kraftkonstanten der Molekülfragmente wiedergeben lassen. O-und N-Substituenten beeinflussen die NO-Kraftkonstante nicht; die SiO-und SiN-Valenzkraftkonstanten sind mit 3,3 mdyn/Å bemerkenswert niedrig.
Vibrational spectra and normal coordinate analysis of some methyl-and trimethylsilylhydroxylamines
The infrared and Raman spectra of the hydroxylamine derivatives quoted above were recorded and frequencies assigned. A normal coordinate treatment of NH2OH,1, 3, 4 and5 showed that the spectra can be explained by a single force field set up by transferring force constants from the different fragments of the molecules. The NO stretching force constant remains unaffected by different substituents. The SiO and SiN stretching force constants are remarkably small (c. 3.3 mdyn/Å).


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