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951.
Alexander J. Blake Binod B. De Wan‐Sheung Li Neil R. Thomas 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(12):m570-m574
In the title compounds, [N‐(phenyl{2‐[N‐(S)‐(2‐picolyl)prolylamino]phenyl}methylene)‐(S)‐phenylalaninato]nickel(II), [Ni(C33H30N4O3)], (I), [N‐(phenyl{2‐[N‐(S)‐(3‐picolyl)prolylamino]phenyl}methylene)‐(S)‐phenylalaninato]nickel(II) hemihydrate, [Ni(C33H30N4O3)]·0.5H2O, (II), and [N‐({2‐[N‐(S)‐ethylprolylamino]phenyl}phenylmethylene)‐(S)‐phenylalaninato]nickel(II), [Ni(C29H29N3O3)], (III), the NiII centres have approximate square‐planar coordination geometries from N3O donor sets. The picolyl N atoms in (I) and (II) are too remote from the metal centres to interact significantly, but the metal coordination geometries experience tetrahedral distortion and/or displacement of the metal centre from the N3O plane. These are linked to conformational differences between the ligands of the symmetry‐independent complexes (Z′ = 2), which in turn are related to molecular packing. In (III), where a less sterically demanding ethyl group replaces the picolyl substituents, there are none of the distortions or displacements seen in (I) and (II). 相似文献
952.
Chun‐Bo Liu Guang‐Bo Che Chuan‐Bi Li Yun‐Cheng Cui 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):m153-m155
An in situ reaction under hydrothermal conditions leads to the formation of the title compound, diaqua(pyridine‐2‐carboxylato)(pyridine‐2,6‐dicarboxylato)indium(II) trihydrate, [In(C6H4NO2)(C7H3NO4)(H2O)2]·3H2O, in which the central InIII atom is seven‐coordinated by one pyridine‐2,6‐dicarboxylate ligand, one pyridine‐2‐carboxylate ligand and two water molecules in a pentagonal–bipyramidal coordination environment. An indium(III)–water chain based on an unusual water pentamer is observed. 相似文献
953.
Yi‐Zhen Tang Hao Sun Ya‐Ru Pan Xiu‐Mei Pan Rong‐Shun Wang 《International journal of quantum chemistry》2007,107(6):1495-1501
The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6‐311++G(d,p)//B3LYP/6‐311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero‐point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6‐311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6‐311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
954.
Wei Sun Yan‐Tuan Li Zhi‐Yong Wu Ning‐Yu Xiao 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(3):m111-m113
In the crystal structure of the title complex, [Ni2(C10H20N4O2)(C12H12N2)2](ClO4)2 or [Ni(dmaeoxd)Ni(dmbp)2](ClO4)2 {H2dmaeoxd is N,N′‐bis[2‐(dimethylamino)ethyl]oxamide and dmbp is 4,4′‐dimethyl‐2,2′‐bipyridine}, the deprotonated dmaeoxd2− ligand is in a cis conformation and bridges two NiII atoms, one of which is located in a slightly distorted square‐planar environment, while the other is in an irregular octahedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd2− ligands interact with each other via C—H⋯O hydrogen bonds and π–π interactions, which results in an extended chain along the c axis. 相似文献
955.
Using the ‘permutation of indices’ method proposed by Kaplan and Fraenkel, we could formulate the density-matrix equations required to fit the temperature-dependent 13C-NMR spectra observed with the title compounds. For 6Li13CHBr2 ( 1 ) and 6Li13CH2SC6H5 ( 2 ) an exchange mechanism is proposed by which monomers interchange C- and Li-atoms via a non-observed dimeric intermediate; the activation parameters of these intermolecular dynamic processes have been found to be ΔH≠ = 10.2 kcal/mol, ΔS≠ = 13.7 cal/mol·K for 1 and ΔH≠ = 11.1 kcal/mol, ΔS≠ = 20.6 cal/mol·K for 2 ((D8)THF as solvent). In the case of (6Li)butyllithium ( 3 ), the observed low-temperature spectra indicate that dimeric ( 3b ) and tetrameric ( 3a ) species are in dynamic equilibrium interchanging the C3HCH2 groups (and THF molecules) bonded to the 6Li-atoms. The relative concentrations of the dimer and of the tetramer have been determined by peak integration or by line-shape fitting; the ‘pseudo’- equilibrium constant, defined by K′eq = [ 3b ]2/[ 3a ], was found to be 2.6·10?2 mol/1 (at ?88°) and corresponds to ΔGR (?88°) = 2 ΔG°f( 3b ) – ΔG°f( 3a ) = 1.34 kcal/mol. The activation parameters of the dynamic process responsible for the exchange were estimated as ΔH≠ = 3.78 kcal/mol and ΔS≠ = ?31.3 cal/mol·K. Tentative interpretation of the thermodynamic and kinetic parameters is given. 相似文献
956.
3-Mercaptopropionic acid monolayer protected gold nanoclusters (MPA-MPCs) were synthesized and characterized by transmission electorn microscopy,UV-Vis spectroscopy,X-ray photoelectron spectroscopy and Fourler transform infrared spectroscopy.The exact value of quantized double-layer capacitance of MPCs in aqueous media was obtained by differential pulse voltammograms. 相似文献
957.
Cetinkaya B Demir S Ozdemir I Toupet L Sémeril D Bruneau C Dixneuf PH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2323-2330
The reaction of electron-rich carbene-precursor olefins containing two imidazolinylidene moieties [(2,4,6-Me(3)C(6)H(2)CH(2))NCH(2)CH(2)N(R)Cdbond;](2) (2a: R=CH(2)CH(2)OMe, 2 b R=CH(2)Mes), bearing at least one 2,4,6-trimethylbenzyl (R=CH(2)Mes) group on the nitrogen atom, with [RuCl(2)(arene)](2) (arene=p-cymene, hexamethylbenzene) selectively leads to two types of complexes. The cleavage of the chloride bridges occurs first to yield the expected (carbene) (arene)ruthenium(II) complex 3. Then a further arene displacement reaction takes place to give the chelated eta(6)-mesityl,eta(1)-carbene-ruthenium complexes 4 and 5. An analogous eta(6)-arene,eta(1)-carbene complex with a benzimidazole frame 6 was isolated from an in situ reaction between [RuCl(2)(p-cymene)](2), the corresponding benzimidazolium salt and cesium carbonate. On heating, the RuCl(2)(imidazolinylidene) (p-cymene) complex 8, with p-methoxybenzyl pendent groups attached to the N atoms, leads to intramolecular p-cymene displacement and to the chelated eta(6)-arene,eta(1)-carbene complex 9. On reaction with AgOTf and the propargylic alcohol HCtbond;CCPh(2)OH, compounds 4-6 were transformed into the corresponding ruthenium allenylidene intermediates (4-->10, 5-->11, 6-->12). The in situ generated intermediates 10-12 were found to be active and selective catalysts for ring-closing metathesis (RCM) or cycloisomerisation reactions depending on the nature of the 1,6-dienes. Two complexes [RuCl(2)[eta(1)-CN(CH(2)C(6)H(2)Me(3)-2,4,6)CH(2)CH(2)N- (CH(2)CH(2)OMe)](C(6)Me(6))] 3 with a monodentate carbene ligand and [RuCl(2)[eta(1)-CN[CH(2)(eta(6)-C(6)H(2)Me(3)-2,4,6)]CH(2)CH(2)N-(CH(2)C(6)H(2)Me(3)-2,4,6)]] 5 with a chelating carbene-arene ligand were characterised by X-ray crystallography. 相似文献
958.
Marguerite Dols Magali Remaud-Simeon René-Marc Willemot Michel Vignon Pierre F. Monsan 《Applied biochemistry and biotechnology》1997,62(1):47-59
Leuconostoc mesenteroides NRRL B-1299 dextransucrase was fractionated into soluble (SGT) and insoluble (IGT) enzyme preparations differing by their dextran content. In spite of this, they displayed the same Km for sucrose (10 g/L) and the same activation energy (35 kJ/mol). But the presence of cells and insoluble dextran led to the IGT behaving like an immobilized enzyme: stabilization against thermal denaturation and diffusional limitations at low substrate concentrations were observed. On the other hand, the behavior of SGT was influenced by the presence, in the preparation, of soluble dextran that reduced enzyme inhibition by excess substrate. SGT and IGT present very different pH profiles. In the presence of 4 g/L of soluble dextran, IGT was activated and displayed the same susceptibility to pH as SGT. The activation of IGT was highly dependent on the nature of the acceptor added but also on the pH of the reaction medium. IGT and SGT synthesize both soluble and insoluble polymer containing α(l → 2), α(l → 3), and α(l → 6) linkages. A larger amount of insoluble dextran is elaborated by SGT. The polymer structures, examined by13C NMR spectrometry, revealed that they differ mainly by their α(l → 3) linkage content (from 0 to 11%). This linkage seems to be partly responsible for the dextran insolubility and can be completely eliminated by carrying out the synthesis of soluble polymer at pH 7.4 with SGT. 相似文献
959.
A theoretical study including full geometry optimizations is carried out at the IMOMM(MP2:MM3) (IMOMM = integrated molecular orbital molecular mechanics) computational level on the [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] systems, the results being compared with available experimental diffraction data, as well as with MP2 results on the model system [ReH(5)(PH(3))(2)(SiH(3))(2)]. A simple scheme for the analysis of the relative weight of different contributions to the "steric" distortion is also proposed and applied to the same [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] species. 相似文献
960.
Pierre Thivollet Jean Gol 《Journal of polymer science. Part A, Polymer chemistry》1973,11(7):1615-1629
Linear polyacroleins prepared by anionic polymerization give the structural repeat units of the types \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--}[{\rm CH}\left( {{\rm CHO}} \right)\hbox{--} {\rm CH}_{\rm 2} {\rm \rlap{--} ], \rlap{--} [CH}_{\rm 2} \hbox{--} {\rm CH}\left( {{\rm CHO}} \right)\rlap{--} ], $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH}\left( {{\rm CH}\hbox {\rm CH}_2 } \right)\hbox{\rm O\rlap{--} ]} $\end{document} without any cyclization. Analysis of these polymers by several methods reveal the nature and amount of each structural species, and an estimation of their distribution along the polymeric chain. 相似文献