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31.
The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been determined by a single-crystal X-ray diffraction study (C(19)H(33)N(4)P, monoclinic system, space group P2(1), a = 9.482(1) ?, b = 11.374(3) ?, c = 9.668(2) ?, beta = 97.16(1) degrees, Z = 2). According to quantum chemical calculations at an RHF level of optimization utilizing the 6-31g(d,p) basis set, 1a has a zwitterionic structure with the negative charge delocalized on the NCN allylic fragment and the positive charge localized at the phosphorus. Heterocycle 1a reacts with water and benzaldehyde affording N-phosphoranylbenzamidine 3 (95% yield) and the expected aza-Wittig adduct 4 (85% yield), respectively. Addition of 1 equiv of methyl trifluoromethanesulfonate and of 2 equiv of BH(3).THF to 1a affords cyclic phosphonium salt 5 (94% yield) and the bis(borane) adduct 6a (90% yield), respectively. Dimethyl acetylenedicarboxylate slowly reacts with 1a giving rise to 1,3,4lambda(5)-diazaphosphinine, 9, in 70% yield. The X-ray crystal structures of products 2,3, and 6a are reported (2: C(26)H(38)N(5)P, monoclinic system, space group C2/c, a = 16.337(8) ?, b = 19.810(2) ?, c = 8.800(2) ?, beta = 117.68(2) degrees, Z = 4. 3: C(19)H(35)N(4)OP, orthorhombic system, space group P2(1)2(1)2(1), a = 9.090(1) ?, b = 12.955(2) ?, c = 17.860(3) ?, Z = 4. 6a: C(19)H(39)B(2)N(4)P, orthorhombic system, space group P2(1)2(1)2(1), a = 10.340(1) ?, b = 13.247(1) ?, c = 16.996(1) ?, Z = 4). 相似文献
32.
Kadish KM Phan TD Giribabu L Shao J Wang LL Thuriere A Van Caemelbecke E Bear JL 《Inorganic chemistry》2004,43(3):1012-1020
Eleven different Ru(2)(4+) and Ru(2)(3+) derivatives are characterized by thin-layer FTIR and UV-visible spectroelectrochemistry under a CO atmosphere. These compounds, which were in-situ electrogenerated from substituted anilinopyridine complexes with a Ru(2)(5+) core, are represented as Ru(2)(L)(4)Cl where L = 2-CH(3)ap, ap, 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, 3,5-F(2)ap, 2,4,6-F(3)ap, or F(5)ap. The Ru(2)(5+) complexes do not axially bind CO while mono- and bis-CO axial adducts are formed for the Ru(2)(4+) and Ru(2)(3+) derivatives, respectively. Six of the eleven investigated compounds exist in a (4,0) isomeric form while five adopt a (3,1) geometric conformation. These two series of compounds thus provide a large enough number of derivatives to examine trends and differences in the spectroscopic data of the two types of isomers in their lower Ru(2)(4+) and Ru(2)(3+) oxidation states. UV-visible spectra of the Ru(2)(4+) derivatives and IR spectra of the Ru(2)(3+) complexes under CO are both isomer dependent, thus suggesting that these data can be used to reliably predict the isomeric form, i.e., (3,1) or (4,0), of diruthenium complexes containing four unsymmetrical substituted anilinopyridinate bridging ligands; this was confirmed by X-ray crystallographic data for seven compounds whose structures were available. 相似文献
33.
In the (MM'O6)infinity chains of the transition-metal magnetic oxides Ca3MM'O6 the MO6 trigonal prisms alternate with the M'O6 octahedra by sharing their triangular faces. In the (Co(2O6)infinity chains of Ca3Co2O6 (M = M' = Co) the spins are coupled ferromagnetically, but in the (FeRhO6)infinity chains of Ca3FeRhO6 (M = Fe, M' = Rh) they are coupled antiferromagnetically. The origin of this difference was probed by carrying out spin-polarized density functional theory electronic band structure calculations for ordered spin states of Ca3Co2O6 and Ca3FeRhO6. The spin state of a (MM'O6)infinity chain determines the occurrence of direct metal-metal bonding between the adjacent trigonal prism and octahedral site transition-metal atoms. The extent of direct metal-metal bonding in the (Co2O6)infinity chains of Ca3Co2O6 is stronger in the intrachain ferromagnetic state than in the intrachain antiferromagnetic state, so that the intrachain ferromagnetic state becomes more stable than the intrachain antiferromagnetic state. Such a metal-metal-bonding-induced ferromagnetism is expected to occur in magnetic insulators and magnetic metals of transition-metal elements in which direct metal-metal bonding can be enhanced by ferromagnetic ordering. In the (FeRhO6)infinity chains of Ca3FeRhO6 the ferromagnetic coupling does not lead to a strong metal-metal bonding and the adjacent spins interact by the Fe-O...O-Fe super-superexchange, hence leading to an antiferromagnetic coupling. 相似文献
34.
Bonhommeau S Bréfuel N Pálfi VK Molnár G Zwick A Salmon L Tuchagues JP Sanchez Costa J Létard JF Paulsen H Bousseksou A 《Physical chemistry chemical physics : PCCP》2005,7(15):2909-2914
A quasi-quantitative photo-induced low-spin (LS)-->high-spin (HS) conversion of FeII ions has been observed in the [Fe(TRIM)2]Cl2 complex by irradiating the sample with blue light (488 nm) at 10 K. The time dependence of the HS-->LS relaxation has been studied between 10 K and 44 K by means of magnetic susceptibility measurements. These relaxation curves could be satisfactorily fitted by mono-exponential decays including tunnelling effect except for temperatures below 30 K. The introduction of a distribution of vibrational frequencies into this model improved significantly the fits in the low-temperature range and gave a good agreement with the experimental data in the whole temperature range suggesting a multi-rate relaxation process in this complex. 相似文献
35.
Factors affecting the electrochemical and spectroelectrochemical properties of diruthenium(III,II) complexes containing four unsymmetrical bridging ligands are reported for seven related compounds which were isolated in one or two of the four possible isomeric forms. The investigated compounds are represented as Ru(2)(2-CH(3)ap)(4)Cl, Ru(2)(2,5-F(2)ap)(4)Cl, Ru(2)(2,6-F(2)ap)(4)Cl, and Ru(2)(2,4,6-F(3)ap)(4)Cl where 2-CH(3)ap, 2,5-F(2)ap, 2,6-F(2)ap, and 2,4,6-F(3)ap are, respectively, the 2-(2-methylanilino)pyridinate anion, the 2-(2,5-difluoroanilino)pyridinate anion, the 2-(2,6-difluoroanilino)pyridinate anion, and the 2-(2,4,6-trifluoroanilino)pyridinate anion. Ru(2)(2-CH(3)ap)(4)Cl and Ru(2)(2,5-F(2)ap)(4)Cl exist only in a (4,0) conformation while Ru(2)(2,4,6-F(3)ap)(4)Cl is present in both (3,1) and (4,0) isomeric forms. Ru(2)(2,6-F(2)ap)(4)Cl also exists in two isomeric forms, but only the (3,1) isomer was generated in sufficient quantities to be isolated and structurally characterized. This series of seven closely related metal-metal bonded complexes thus provides the first possibility to systematically examine how differences in position and number of the electron-donating or electron-withdrawing groups on the anionic bridging ligands might be related to the electronic properties and structural features of the compound as well as the type and number of geometric isomers which are formed. Each diruthenium derivative undergoes three one-electron transfers in CH(2)Cl(2) containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). The first reduction and first oxidation products were characterized by thin-layer UV-vis spectroelectrochemistry, and the spectroscopic data, along with E(1/2) values, were then related via linear free energy relationships to the type of isomer and/or position of the electron-donating or electron-withdrawing substituents on the anionic ap bridge. The electrogenerated Ru(2)(6+) and Ru(2)(4+) forms of the compounds were assigned on the basis of electrochemical and UV-vis spectroscopic data as having the electronic configuration sigma(2)pi(4)delta(2)pi(2) and sigma(2)pi(4)delta(2)pi(3)delta, respectively, and seemed to be independent of the isomer type ((3,1) or (4,0)). The spectral and electrochemical properties of the compounds both vary substantially as a function of the isomer type, but this is not reflected in the structural features of the compounds which are within the range of what is seen for other Ru(2)(5+) species described in the literature. The Ru-Ru bond lengths of the four structurally characterized (4,0) isomers of the ap complexes range from 2.275 to 2.296 A while those of the three structurally characterized (3,1) isomers of ap derivatives fall in the range 2.284-2.286 A and show no significant difference among the three compounds. The Ru-Cl bond lengths of the (3,1) isomers do not vary significantly with the bridging ligand and range from 2.458 to 2.471 A whereas those of the (4,0) isomers range from 2.437 to 2.487 A and show larger variations among the compounds. The Ru-Ru-Cl bond angle is virtually independent of the bridging ligand in the case of the (4,0) isomers but decreases with the electron-withdrawing effect of the substituent in the case of the (3,1) isomers. 相似文献
36.
Fort S Birikaki L Dubois MP Antoine T Samain E Driguez H 《Chemical communications (Cambridge, England)》2005,(20):2558-2560
Oligosaccharidic moieties of GM(2) and GM(3) gangliosides bearing an allyl or a propargyl aglycon, are efficiently biosynthesized on the gram scale by growing metabolically engineered Escherichia coli cells in the presence of the corresponding lactoside acceptors and sialic acid. 相似文献
37.
Kadish KM Wang LL Thuriere A Giribabu L Garcia R Van Caemelbecke E Bear JL 《Inorganic chemistry》2003,42(25):8309-8319
Three Ru2(5+) diruthenium complexes, (4,0) Ru2(2-CH3ap)4Cl, (3,1) Ru2(2-Fap)4Cl, and (3,1) Ru2(2,4,6-F3ap)4Cl where ap is the 2-anilinopyridinate anion, were examined as to their electrochemical and spectroelectrochemical properties in five different nonaqueous solvents (CH2Cl2, THF, PhCN, DMF, and DMSO). Each compound undergoes a single one-electron metal-centered oxidation in THF, DMF, and DMSO and two one-electron metal-centered oxidations in CH2Cl2 and PhCN. The three diruthenium complexes also undergo two reductions in each solvent except for CH2Cl2, and these electrode processes are assigned as Ru2(5+/4+) and Ru2(4+/3+). Each neutral, singly reduced, and singly oxidized species was characterized by UV-vis thin-layer spectroelectrochemistry, and the data are discussed in terms of the most probable electronic configuration of the compound in solution. The three neutral complexes contain three unpaired electrons as indicated by magnetic susceptibility measurements using the Evans method (3.91-3.95 muB), and the electronic configuration is assigned as sigma2pi4delta2pi(*2)delta, independent of the solvent. The three singly oxidized compounds have two unpaired electrons in CD2Cl2, DMSO-d6, or CD3CN (2.65-3.03 muB), and the electronic configuration is here assigned as sigma2pi4delta2pi(*2). The singly reduced compound also has two unpaired electrons (2.70-2.80 muB) in all three solvents, consistent with the electronic configuration sigma2pi4delta2pi(*2)delta(*2) or sigma2pi4delta2pi(*3)delta*. Finally, the overall effect of solvent on the number of observed redox processes is discussed in terms of solvent binding, and several formation constants were calculated. 相似文献
38.
Jonathan Pansieri Igor A. Iashchishyn Hussein Fakhouri Lucija Ostoji Mantas Malisauskas Greta Musteikyte Vytautas Smirnovas Matthias M. Schneider Tom Scheidt Catherine K. Xu Georg Meisl Tuomas P. J. Knowles Ehud Gazit Rodolphe Antoine Ludmilla A. Morozova-Roche 《Chemical science》2020,11(27):7031
The mechanism of amyloid co-aggregation and its nucleation process are not fully understood in spite of extensive studies. Deciphering the interactions between proinflammatory S100A9 protein and Aβ42 peptide in Alzheimer''s disease is fundamental since inflammation plays a central role in the disease onset. Here we use innovative charge detection mass spectrometry (CDMS) together with biophysical techniques to provide mechanistic insight into the co-aggregation process and differentiate amyloid complexes at a single particle level. Combination of mass and charge distributions of amyloids together with reconstruction of the differences between them and detailed microscopy reveals that co-aggregation involves templating of S100A9 fibrils on the surface of Aβ42 amyloids. Kinetic analysis further corroborates that the surfaces available for the Aβ42 secondary nucleation are diminished due to the coating by S100A9 amyloids, while the binding of S100A9 to Aβ42 fibrils is validated by a microfluidic assay. We demonstrate that synergy between CDMS, microscopy, kinetic and microfluidic analyses opens new directions in interdisciplinary research.Templating mechanism of S100A9 amyloids on Aβ fibrillar surfaces during amyloid co-aggregation process was revealed by synergy of biophysical methods including charge detection mass spectrometry, microscopy, kinetic and microfluidic analyses. 相似文献
39.
40.
Jacques Le Moigne Armand Soldera Daniel Guillon Antoine Skoulios 《Liquid crystals》2013,40(6):627-639
Abstract Acetylenic and diacetylenic mesomorphic monomers have been prepared in order to obtain long conjugated polymers able to give high non-linear optical hyperpolarizabilities. Here we report the synthesis of such monomers incorporating cholesteryl and methoxybiphenyl groups; their structural and thermal behaviour are described. The occurrence of mesophases in the acetylenic and diacetylenic derivatives is discussed as a function of the spacer length and of the size of the mesogen moiety. The diacetylenic derivatives containing the methoxybiphenyl groups do not exhibit any liquid-crystalline behaviour but are able to polymerize under U.V. radiation. 相似文献