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51.
Lionel Salmon Pierre Thury Michel Ephritikhine Bernardo Masci 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(1):m27-m29
The title compound, [UO2(C33H38N2O2)2](CF3SO3)2·2C5H5N, has been obtained by reaction of UIV trifluoromethanesulfonate with p‐tert‐butyltetrahomodioxacalix[4]arene in pyridine. The uranyl ion lies on an inversion centre and is bound to two O atoms from each diphenoxide ligand, which gives the usual square‐planar equatorial environment. The zwitterionic diphenoxide species results from nucleophilic attack by pyridine on the benzylic ether C atoms of the homooxacalixarene, assisted by initial U coordination to the ether groups, with subsequent metal oxidation giving the uranyl moiety. 相似文献
52.
Dr. Emilio Brunetti Dr. Lionel Marcelis Dr. Fedor E. Zhurkin Prof. Michel Luhmer Prof. Ivan Jabin Prof. Olivia Reinaud Prof. Kristin Bartik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(55):13730-13738
In this study, the ligand exchange mechanism at a biomimetic ZnII centre, embedded in a pocket mimicking the possible constrains induced by a proteic structure, is explored. The residence time of different guest ligands (dimethylformamide, acetonitrile and ethanol) inside the cavity of a calix[6]arene-based tris(imidazole) tetrahedral zinc complex was probed using 1D EXchange SpectroscopY NMR experiments. A strong dependence of residence time on water content was observed with no exchange occurring under anhydrous conditions, even in the presence of a large excess of guest ligand. These results advocate for an associative exchange mechanism involving the transient exo-coordination of a water molecule, giving rise to 5-coordinate ZnII intermediates, and inversion of the pyramid at the ZnII centre. Theoretical modelling by DFT confirmed that the associative mechanism is at stake. These results are particularly relevant in the context of the understanding of kinetic stability/lability in Zn proteins and highlight the key role that a single water molecule can play in catalysing ligand exchange and controlling the lability of ZnII in proteins. 相似文献
53.
Routaboul C Dumas L Gautier-Luneau I Vergne J Maurel MC Décout JL 《Chemical communications (Cambridge, England)》2002,(10):1114-1115
A remarkable stereoselective reaction of methylglyoxal with 2-aminopyridine, the nucleic base adenine and adenine nucleosides leads in good yield to heterocycles of a new family in water under mild conditions and should be of interest in the understanding of the biological effects of methylglyoxal which is toxic, mutagenic and involved in diabetic complications. 相似文献
54.
Gobeaux F Fay N Tarabout C Mériadec C Meneau F Ligeti M Buisson DA Cintrat JC Nguyen KM Perrin L Valéry C Artzner F Paternostre M 《Journal of the American Chemical Society》2012,134(1):723-733
Among noncovalent forces, electrostatic ones are the strongest and possess a rather long-range action. For these reasons, charges and counterions play a prominent role in self-assembly processes in water and therefore in many biological systems. However, the complexity of the biological media often hinders a detailed understanding of all the electrostatic-related events. In this context, we have studied the role of charges and counterions in the self-assembly of lanreotide, a cationic octapeptide. This peptide spontaneously forms monodisperse nanotubes (NTs) above a critical concentration when solubilized in pure water. Free from any screening buffer, we assessed the interactions between the different peptide oligomers and counterions in solutions, above and below the critical assembly concentration. Our results provide explanations for the selection of a dimeric building block instead of a monomeric one. Indeed, the apparent charge of the dimers is lower than that of the monomers because of strong chemisorption. This phenomenon has two consequences: (i) the dimer-dimer interaction is less repulsive than the monomer-monomer one and (ii) the lowered charge of the dimeric building block weakens the electrostatic repulsion from the positively charged NT walls. Moreover, additional counterion condensation (physisorption) occurs on the NT wall. We furthermore show that the counterions interacting with the NTs play a structural role as they tune the NTs diameter. We demonstrate by a simple model that counterions adsorption sites located on the inner face of the NT walls are responsible for this size control. 相似文献
55.
Dr. Hongpeng Jia Belinda Schmid Dr. Shi‐Xia Liu Michael Jaggi Philippe Monbaron Dr. Sheshanath V. Bhosale Shadi Rivadehi Prof. Steven J. Langford Dr. Lionel Sanguinet Dr. Eric Levillain Dr. Mohamed E. El‐Khouly Prof. Ysushi Morita Prof. Shunichi Fukuzumi Prof. Silvio Decurtins 《Chemphyschem》2012,13(14):3370-3382
A tetrathiafulvalene (TTF) donor is annulated to porphyrins (P) via quinoxaline linkers to form novel symmetric P–TTF–P triads 1 a – c and asymmetric P–TTF dyads 2 a , b in good yields. These planar and extended π‐conjugated molecules absorb light over a wide region of the UV/Vis spectrum as a result of additional charge‐transfer excitations within the donor–acceptor assemblies. Quantum‐chemical calculations elucidate the nature of the electronically excited states. The compounds are electrochemically amphoteric and primarily exhibit low oxidation potentials. Cyclic voltammetric and spectroelectrochemical studies allow differentiation between the TTF and porphyrin sites with respect to the multiple redox processes occurring within these molecular assemblies. Transient absorption measurements give insight into the excited‐state events and deliver corresponding kinetic data. Femtosecond transient absorption spectra in benzonitrile may suggest the occurrence of fast charge separation from TTF to porphyrin in dyads 2 a , b but not in triads 1 a – c . Clear evidence for a photoinduced and relatively long lived charge‐separated state (385 ps lifetime) is obtained for a supramolecular coordination compound built from the ZnP–TTF dyad and a pyridine‐functionalized C60 acceptor unit. This specific excited state results in a (ZnP–TTF)?+ ??? (C60py)?? state. The binding constant of ZnII ??? py is evaluated by constructing a Benesi–Hildebrand plot based on fluorescence data. This plot yields a binding constant K of 7.20×104 M ?1, which is remarkably high for bonding of pyridine to ZnP. 相似文献
56.
57.
Hong-Peng Jia John C. Forgie Shi-Xia Liu Lionel Sanguinet Eric Levillain Franck Le Derf Marc Sallé Antonia Neels Peter J. Skabara Silvio Decurtins 《Tetrahedron》2012,68(5):1590-1594
A tetrathiafulvalene donor has been annulated to 2,3-di(1H-2-pyrrolyl)quinoxaline affording a new chemosensor 1, which shows a unique optical selectivity and reactivity for the fluoride ion over other anions in CH2Cl2 leading to a colorimetric response. Electrochemical polymerization of 1 occurred in the presence of fluoride. 相似文献
58.
Romero I Dubois L Collomb MN Deronzier A Latour JM Pécaut J 《Inorganic chemistry》2002,41(7):1795-1806
Reactions of Mn(II)(PF(6))(2) and Mn(II)(O(2)CCH(3))(2).4H(2)O with the tridentate facially capping ligand N,N-bis(2-pyridylmethyl)ethylamine (bpea) in ethanol solutions afforded the mononuclear [Mn(II)(bpea)](PF(6))(2) (1) and the new binuclear [Mn(2)(II,II)(mu-O(2)CCH(3))(3)(bpea)(2)](PF(6)) (2) manganese(II) compounds, respectively. Both 1 and 2 were characterized by X-ray crystallographic studies. Complex 1 crystallizes in the monoclinic system, space group P2(1)/n, with a = 11.9288(7) A, b = 22.5424(13) A, c =13.0773(7) A, alpha = 90 degrees, beta = 100.5780(10 degrees ), gamma = 90 degrees, and Z = 4. Crystals of complex 2 are orthorhombic, space group C222(1), with a = 12.5686(16) A, b = 14.4059(16) A, c = 22.515(3) A, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, and Z = 4. The three acetates bridge the two Mn(II) centers in a mu(1,3) syn-syn mode, with a Mn-Mn separation of 3.915 A. A detailed study of the electrochemical behavior of 1 and 2 in CH(3)CN medium has been made. Successive controlled potential oxidations at 0.6 and 0.9 V vs Ag/Ag(+) for a 10 mM solution of 2 allowed the selective and nearly quantitative formation of [Mn(III)(2)(mu-O)(mu-O(2)CCH(3))(2)(bpea)(2)](2+) (3) and [Mn(IV)(2)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](3+) (4), respectively. These results have shown that each substitution of an acetate group by an oxo group is induced by a two-electron oxidation of the corresponding dimanganese complexes. Similar transformations have been obtained if 2 is formed in situ either by direct mixing of Mn(2+) cations, bpea ligand, and CH(3)COO(-) anions with a 1:1:3 stoichiometry or by mixing of 1 and CH(3)COO(-) with a 1:1.5 stoichiometry. Associated electrochemical back-transformations were investigated. 2, 3, and the dimanganese [Mn(III)Mn(IV)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](2+) analogue (5) were also studied for their ability to disproportionate hydrogen peroxide. 2 is far more active compared to 3 and 5. The EPR monitoring of the catalase-like activity has shown that the same species are present in the reaction mixture albeit in slightly different proportions. 2 operates probably along a mechanism different from that of 3 and 5, and the formation of 3 competes with the disproportionation reaction catalyzed by 2. Indeed a solution of 2 exhibits the same activity as 3 for the disproportionation reaction of a second batch of H(2)O(2) indicating that 3 is formed in the course of the reaction. 相似文献
59.
A theoretical study of SiH(4) activation by Cp(2)LnH complexes for the entire series of lanthanides has been carried out at the DFT-B3PW91 level of theory. The reaction paths corresponding to H/H exchange and silylation, formation of Cp(2)Ln(SiH(3)), have been computed. They both occur via a single-step sigma-bond metathesis mechanism. For the athermal H/H exchange reaction, the calculated activation barrier averages 1.8 kcal.mol(-)(1) relative to the precursor adduct Cp(2)LnH(eta(2)-SiH(4)) for all lanthanide elements. The silylation path is slightly exogenic (DeltaE approximately -6.5 kcal.mol(-1)) with an activation barrier averaging 5.2 kcal.mol(-1) relative to the precursor adduct where SiH(4) is bonded by two Si-H bonds. Both pathways are therefore thermally accessible. The H/H exchange path is calculated to be kinetically more favorable whereas the silylation reaction is thermodynamically preferred. The reactivity of this familly of lanthanide complexes with SiH(4) contrasts strongly with that obtained previously with CH(4). The considerably lower activation barrier for silylation relative to methylation is attributed to the ability of Si to become hypervalent. 相似文献
60.
Mark S. Mashuta Lionel Cheruzel Robert M. Buchanan 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):o629-o631
Cocrystallization of a polyimidazole compound with boric acid results in the formation of the title compound, C15H21N7·B(OH)3, which has an extensive hydrogen‐bonding network. The O?N(im) separations (im is imidazole) range from 2.6991 (15) to 2.7914 (14) Å, with O—H?N angles ranging from 170.6 (18) to 175 (2)°. In addition, symmetry‐related boric acid molecules form intermolecular hydrogen bonds, with an O?O distance of 2.7582 (14) Å, and symmetry‐related imidazole groups form π–π stacks, with a centroid‐to‐centroid separation of 3.533 Å. 相似文献