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31.
Grotjahn DB Van S Combs D Lev DA Schneider C Incarvito CD Lam KC Rossi G Rheingold AL Rideout M Meyer C Hernandez G Mejorado L 《Inorganic chemistry》2003,42(10):3347-3355
Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions. 相似文献
32.
The structural parameters of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), (CH2NNO2)3, 1,3-dinitro-1,3-diazacyclopentane (DDCP), CH2(CH2NNO2)2, andN-nitropyrrolidine (NP), (CH2)4NNO2, have been determined by electron diffraction.The six-membered ring of RDX has a chair form with axial positions of the nitro groups and close to planar bond geometry of the amine nitrogen atoms. The overallC
3 symmetry of the molecule is in agreement with the experimental data.The conformation of the five-membered ring in DDCP is a half-chair ofC
2 symmetry, while that in NP is an envelope ofC
S symmetry. The nitro groups are in equatorial positions in both molecules. The conformations of pyrrolidine and imidazolidine cycles show interesting features.The pyramidal geometry of the amine nitrogen atom bonds flattens in going from pyrrolidine andN-chloropyrrolidine to NP and DDCP and then to RDX and to dimethylnitramine (DMNA), (CH3)2NNO2. 相似文献
33.
34.
Lev Vaidman 《Foundations of Physics》1996,26(7):895-906
A brief review of the attempts to define elements of reality in the framework of quantum theory is presented. It is noted that most definitions of elements of reality have in common the feature to be a definite outcome of some measurement. Elements of reality are extended to pre- and post- selected systems and to measurements which fulfill certain criteria of weakness of the coupling. Some features of the newly introduced concepts are discussed.This research was supported in part by grant 614/65 of the Basic Research Foundation (administered by the Israel Academy of Sciences and Humanities. 相似文献
35.
Vsevolod F. Lev 《Combinatorica》1996,16(4):587-590
In this note the method of [5] and a result from [3] are combined to treat the following classical problem: Given a finite setA and an infinite sequenceS (both inZ), what is the minimal number of elements ofA whose sum lies inS? We obtain an upper bound depending only on the densities ofA andS (but not on their arithmetic nature). 相似文献
36.
The quadrupole resonance spectra and the quadrupole spin-lattice relaxation times of the35Cl nuclei are correlated with the molecular structures of the two chlorine-containing diazadienes CCl3CCl=NCCl=NC6H5 and CCl3CCl=NCCl=NCCl2CCl3. The monotropic polymorphism found in the case of the second crystal is discussed.Perm State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 2, pp. 84–87, March–April, 1993. 相似文献
37.
A phenanthroline ligand has been covalently modified at the 2 and 9 positions by an aminophenylhexamolybdate substituent. The 1H NMR spectrum indicated a strong electron-withdrawing effect of the hexamolybdate (Mo6O19(2-)) moiety on the phenanthroline ligand. UV-vis and cyclic voltammetry showed extended conjugation of the hybrid phenanthroline-polyoxometalate compound and the possibility of easy oxidation of the extended phenanathroline ligand. Further EPR experiments provided strong evidence for an intramolecular charge-transfer process with the formation of a phenanthroline cation radical and a reduced hexamolybdate. 相似文献
38.
Intramolecular cyclization of acyl(ethoxycarbonyl)keteneN-benzoylaminals in boiling Ph2O gives 5-acyl-4-amino-2-phenyl-1,3-oxazin-6-ones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1322–1323, July, 1995.This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-08964). 相似文献
39.
The reaction of o-aminobenzohydroxamic acid with aliphatic, aromatic, or heterocyclic aldehydes leads to the formation of
derivatives of 3-hydroxy-1,2-dihydroquinazolin-4-one.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 115–117, January, 1997. 相似文献
40.
A new type of inorganic biosensor is introduced. The sensor comprises glucose oxidase enzymes encapsulated in a sol-gel-derived
Prussian blue-silicate hybrid network. Glucose is detected by the biocatalytic reduction of oxygen followed by catalytic reduction
of hydrogen peroxide by the Prusian blue catalyst. The sol-gel silicate entails a rigid encapsulating matrix, the Prussian
blue provides chemical catalysis and charge mediation from the reduction site to the supporting electrode, and the enzyme
is responsible for the biocatalysis. The feasibility of a dual optical/electrochemical mode of analysis is also demonstrated. 相似文献