Search results for "Substituent"
showing 10 items of 353 documents
Ligand Design for Heterobimetallic Single-Chain Magnets: Synthesis, Crystal Structures, and Magnetic Properties of MIICuII (M=Mn, Co) Chains with Ste…
2006
Two new series of neutral ox-amato-bridged heterobimetallic chains of general formula [MCu(L x ) 2 ]- m DMSO (m=0-4) (L 1 =N-2-methyl-phenyloxamate, M=Mn (1a) and Co (1 b); L2 = N-2,6-dimethylphenyloxamate, M=Mn (2a) and Co (2b); L 3 = N-2,4,6-trimethylphenyloxamate, M= Mn (3a) and Co (3b)) have been prepared by reaction between the corresponding anionic oxamatocopper(II) complexes [Cu(L x ) 2 ] 2- with Mn 2+ or Co 2+ cations in DMSO. The crystal structures of [CoCu(L 2 ) 2 (H 2 O) 2 ] (2b') and [CoCu(L 3 ) 2 (H 2 O) 2 ]·4H 2 O (3b') have been solved by single-crystal X-ray diffraction methods. Compounds 2b' and 3b' adopt zigzag and linear chain structures, respectively. The intrachain Cu··…
Characterization of electronic properties of the Cr(CO)3 group in chromium, tricarbonyl [3-[(η6-aryl)methylene]-Z-1(3H)-isobenzofuranones] using spec…
1999
Abstract The IR, 13C- and 17O-NMR spectral characteristics of the Cr(CO)3 group in a series of eight chromium, tricarbonyl[3-[(η6-aryl)methylene]-Z-1(3H)-isobenzofuranones] were correlated mutually as well as with theoretical data obtained by optimized MMX force-field and EHT calculations. The net charges on the carbon and oxygen atoms of the CO group and their differences were found as the most appropriate quantitative characteristics for the electronic properties of the Cr(CO)3 group. Using the results of the previously reported linear correlations, the electron-withdrawing effect of the PhCr(CO)3 moiety, weakened by the back-donation effect, was estimated as σα≅0.45 on the scale of Hamm…
A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σp in [3+2] Cycloaddition Reactions of Aryl Azide/A…
2016
The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT) descriptor evaluated at the ground state of the molecules—shows a good linear relationship with the Hammett substituent constants σp. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components.
Heterocyclic photorearrangements. Photochemical behaviour of some 3,5-disubstituted 1,2,4-oxadiazoles in methanol at 254 nm
1988
Photochemical behaviour of some 3,5-disubstituted 1,2,4-oxadiazoles in methanol at 254 nm has been investigated. Ring photoisomerization to the 1,3,4-oxadiazole heterocycle or formation of open chain compounds involving the nucleophilic solvent was shown to depend on the nature and the position of the substituent. Photoinduced ring closure into the benzimidazole system, involving a 3-N-phenylamino side chain sequence and a photolytic intermediate of the oxadiazole heterocycle, is also reported.
ChemInform Abstract: Heterocyclic Photorearrangements. Photochemical Behaviour of Some 3,5-Disubstituted 1,2,4-Oxadiazoles in Methanol at 254 nm.
1989
Photochemical behaviour of some 3,5-disubstituted 1,2,4-oxadiazoles in methanol at 254 nm has been investigated. Ring photoisomerization to the 1,3,4-oxadiazole heterocycle or formation of open chain compounds involving the nucleophilic solvent was shown to depend on the nature and the position of the substituent. Photoinduced ring closure into the benzimidazole system, involving a 3-N-phenylamino side chain sequence and a photolytic intermediate of the oxadiazole heterocycle, is also reported.
Dependence of the Substituent Effect on Solvent Properties
2018
The influence of a solvent on the substituent effect (SE) in 1,4-disubstituted derivatives of benzene (BEN), cyclohexa-1,3-diene (CHD), and bicyclo[2.2.2]octane (BCO) is studied by the use of polarizable continuum model method. In all X–R–Y systems for the functional group Y (NO2, COOH, OH, and NH2), the following substituents X have been chosen: NO2, CHO, H, OH, and NH2. The substituent effect is characterized by the charge of the substituent active region (cSAR(X)), substituent effect stabilization energy (SESE), and substituent constants σ or F descriptors, the functional groups by cSAR(Y), whereas π-electron delocalization of transmitting moieties (BEN and CHD) is characterized by a geo…
How far the substituent effects in disubstituted cyclohexa-1,3-diene derivatives differ from those in bicyclo[2.2.2]octane and benzene?
2018
Substituents effects in cyclic diene derivatives are studied using quantum chemical modeling and compared to the corresponding effects in aromatic (benzene) and fully saturated (bicyclo[2.2.2]octane) compounds. In particular, electronic properties of the fixed group Y in a series of 3- and 4-X-substituted cyclohexa-1,3-diene-Y derivatives (where Y = NO2, COOH, COO− OH, O−, NH2, and X = NMe2, NH2, OH, OMe, Me, H, F, Cl, CF3, CN, CHO, COMe, CONH2, COOH, NO2, NO) are examined using the B3LYP/6-311++G(d,p) method. For this purpose, quantum chemistry models of the substituent effect: cSAR (charge of the substituent active region) and SESE (substituent effect stabilization energy) as well as trad…
New cycloaddition reactions of 1-phenyl-4-vinylpyrazole
1986
Abstract 1-Phenyl-4-vinylpyrazole reacts with methyl propiolate and N-phenylmaleimide giving via the Diels-Alder 1:1 adducts, products (4) and (8), and also the 1:2 adducts (5), (6) and (9) resulting from an “ene” reaction of the initially forced cycloadducts. The obtention of the adducts (5) and (6) in equimolecular amounts is a good example of the non-regioselective character of the “ene” reaction. The reaction with tetracyanoethylene takes place through the olefinic substituent giving the π2 + π2 adduct (10).
Polyazapodands Derived from Biphenyl. Study of their Behaviour as Conformationally Regulated Fluorescent Sensors
2004
Eight new polyazapodands containing a 4,4′-substituted biphenyl moiety have been synthesised. Four (7, 8, 9 and 11) are functionalised on positions 4 and 4′ with a nitro group and four (1, 2, 3 and 10) with a dimethylamino substituent. Comparison of the emission behaviour of 1, 2, 3 with that of the reference compounds 10 and tetramthylbenzidine, clearly suggests that a modification in the dihedral angle between the biphenyl rings is an important factor in determining the fluorescent response of the molecule. The fluorescence is pH dependent, due to the formation of intramolecular hydrogen bonds between protonated aliphatic nitrogens and a carbonyl oxygen, which influences the aforementione…
Synthesis and fluorescence emission of neutral and anionic di- and tetra-carboranyl compounds
2011
A new family of photoluminescent neutral and anionic di-carboranyl and tetra-carboranyl derivatives have been synthesized and characterized. The reaction of α,α'-bis(3,5-bis(bromomethyl)phenoxy-m-xylene with 4 equiv. of the monolithium salt of 1-Ph-1,2-C(2)B(10)H(11) or 1-Me-1,2-C(2)B(10)H(11) gives the neutral tetracarboranyl-functionalized aryl ether derivatives closo-1 and closo-2, respectively. The addition of the monolithium salt of 1-Ph-1,2-closo-C(2)B(10)H(11) to α,α,'-dibromo-m-xylene or 2,6-dibromomethyl-pyridine gives the corresponding di-carboranyl derivatives closo-3 and closo-4. These compounds, which contain four or two closo clusters, were degraded using the classical method,…