Electrophilic Aromatic Substitution of Groups other than Hydrogen. Part I: Ipso Factors and Rate-Limiting Steps in Dehalogenations by Diazonium Ions. 26th communication on diazo coupling reactions

The rates of substitution of the group X in 1-X-2-naphthol-6-sulfonic acids (X = H, Cl, Br, and I) by p-chlorobenzenediazonium ions in aqueous solution have been measured. The rates of the halogenated naphthols relative to that of the parent compound (X = H) are 0.0070:0.0089:0.149 for X = Cl, Br, and I respectively. The reaction of 1-bromo-2-naphthol-6-sulfonic acid is catalysed by thiosulfate ions; the relative rate observed for this compound does not, therefore, represent the ipso factor. It is postulated that in its substitution the release of the electrofugal leaving group (Br^⊕) is rate-limiting.     

A novel spectroscopy using ultrafast two-pulse excitation of large polyatomic molecules

A first infrared pulse at frequency ν₁ interacts with vibrational states in S₀ and a second visible pulse at ν₂ promotes the excited molecules to the S₁ state from where they fluoresce. Tuning the frequency ν₂ over 600 cm^?1 allows the observation of a detailed spectrum which gives information on vibrational states in S₀ and on vibronic states in S₁ together with corresponding Franck—Condon factors. The spectra differ drastically from the common broad and featureless absorption and fluorescence bands.     

Kinetische und mechanistische untersuchungen von übergangsmetallkomplex-reaktionen : IX. Substitution von CO durch PPh3 in aminocarbinkomplexen: Präparative und kinetische untersuchungen

Pentacarbonyl(diethylaminocarbyne)chromium tetrafluoroborate, [(CO)₅₋ CrCNEt₂]BF₄ (I), reacts with PPh₃ with substitution of CO and formation of trans-tetracarbonyl(diethylaminocarbyne)triphenylphosphanechromium tetra-fluoroborate, trans-[PPh₃(CO)₄CrCNEt₂]BF₄ (III). Substitution of CO by PPh₃ in neutral trans-tetracarbonyl(halo)(diethylaminocarbyne)chromium complexes, trans-X(CO)₄CrCNEt₂ (IVa: X = Br, IVb: X = I), leads in a reversible reaction to the corresponding tricarbonyl complexes, mer-X(PPh₃)(CO)₃₋ CrNEt₂ (V), PPh₃ occupying the cis-position to the carbyne ligand. With PPh₃ in large excess both reactions follow a first-order rate law. This as well as the activation parameters (ΔH≠ = 104–113 kJ mol⁻¹, ΔS≠ = 64–71 J mol⁻¹ K⁻¹) indicate a dissociative mechanism.     

Synthesis,crystal structure,magnetism, and absorption spectra of A2UX5 Type Halides (A = K,Rb; X = Cl,Br, I)

The ternary uranium(III) halides A₂UX₅ (A = K, Rb; X = Cl, Br, I) have been prepared from the binary components AX and UX₃ in sealed tantalum containers. According to their Guinier X-ray powder patterns, they all crystallize with the K₂PrCl₅/Y₂HfS₅ type of structure. Lattice constants for ambient temperature are reported. Single-crystal structure refinemens were undertaken for K₂UI₅ and Rb₂UCl₅. Magnetic susceptibility data were recorded with a SQUID magnetometer from liquid helium to room temperature. One-dimensional (intrachain) and three-dimensional antiferromagnetic ordering occur at low temperatures dependent upon the U³⁺? U³⁺ distance. Absorption spectra were recorded between 4 000 and 28 000 cm^?1. They show f—f transitions typical for U³⁺ and, depending on the halide, very strong f—d transitions above 14 000 to 15 000 cm^?1, respectively.     

Compactification of a myelin mimetic Langmuir monolayer upon adsorption and unfolding of myelin basic protein

The surface shear viscosity of a myelin mimetic Langmuir monolayer is investigated upon adsorption of myelin basic protein (MBP). We measure an increase of the surface shear viscosity at picomolar concentrations of the protein, suggesting that the globular conformation of MBP changes upon adsorption at the monolayer. The conformational change enables hydrodynamic interactions of the proteins, with a typical separation of hundreds of nanometers. This unfolding is essential for the compactification of the myelin sheath, serving an enhanced saltatory signal transduction in vertebrates. The viscometry used extends the sensitivity of standard surface viscometers toward lower viscosities.     

Pyryliumverbindungen—XII: Synthesen und eigenschaften von 1,2-benzoxalenen (indeno[2,1-b]pyranen)

Pseudoazulenes of the 1,2-benzoxalene type C (indeno[2,1-b]pyranes) are accessible by two new ways: The title compounds 1–10 were synthesized by acid catalysed cyclodeamination of ketovinylated 2-piperidinoindenes F, the compounds 13–36 by deprotonation of 9H-indeno[2,1-b]pyrylium salts L obtained from indan-2-ones and β-diketones. The aromatic nature of the pseudoazulene system is described in terms of various physical and theoretical results (electronic spectra, resonance energies, HMO calculations).     

Lifetime of 2s2p 23s 3 P in N II and other allowed triplet transitions

Systematic transition calculations have been performed for all triplet decay channels from 2s2p ²3s ³ P of N II. The lifetime of 0.505 ns compares favourably with experiment. Transitions in absorption from the 2s ²2p ^{2 3} P ground state have also been determined along with a number of other triplet transitions. Length and velocity forms of thef-value are in agreement at the 2–3% level for most transitions.     

Alkyl and aryl substituted corroles. 1. Synthesis and characterization of free base and cobalt containing derivatives. x-ray structure of (Me(4)Ph(5)Cor)Co(py)(2)

The synthesis, spectroscopic properties, and electrochemistry of six different alkyl- and aryl-substituted Co(III) corroles are presented. The investigated compounds contain methyl, ethyl, phenyl, or substituted phenyl groups at the eight beta-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-meso position of the macrocycle. Each cobalt corrole undergoes four reversible oxidations in CH(2)Cl(2) containing 0.1 M tetra-n-butylammonium perchlorate and exists as a dimer in its singly and doubly oxidized forms. The difference in potential between the first two oxidations is associated with the degree of interaction between the two corrole units of the dimer and ranges from an upper value of 0.62 V, in the case of (Me(6)Et(2)Cor)Co, to a lower value of about 0.17 V, in the case of four compounds which have a phenyl group located at the 10-meso position of the macrocycle. These Co(III) corroles strongly coordinate two pyridine molecules or one carbon monoxide molecule in CH(2)Cl(2) media, and ligand binding constants were evaluated using spectroscopic and electrochemical methods. The structure of (Me(4)Ph(5)Cor)Co(py)(2) was also determined by X-ray diffraction. Crystal data: (Me(4)Ph(5)Cor)Co(py)(2).3CH(2)Cl(2).H(2)O, orthorhombic, a = 19.5690(4) A, b = 17.1070(6) A, c = 15.9160(6) A, V = 5328.2(5) A(3), space group Pna2(1), Z = 2, 35 460 observations, R(F) = 0.069.     

Cu(OAc)2-catalyzed N-arylations of sulfoximines with aryl boronic acids

[reaction: see text] A simple and mild copper salt-catalyzed N-arylation of sulfoximines in high yields is reported. Cu(OAc)(2) activates aryl boronic acids for the reaction with NH-sulfoximines without additional base or heating. Furthermore, this new method allows the preparation of N-arylated sulfoximines, which have previously been more difficult to access.     

On the uniqueness of symmetric bases in finite dimensional Banach spaces

Suppose{e _i} _i=1 ⁿ and{f _i} _i=1 ⁿ are symmetric bases of the Banach spacesE andF. Letd(E,F)≦C andd(E,l _n ² )≧n' for somer>0. Then there is a constantC _r=C_r(C)>0 such that for alla _i∈Ri=1,...,n $$C_r^{ - 1} \left\| {\sum\limits_{i = 1}^n {a_i e_i } } \right\| \leqq \left\| {\sum\limits_{i = 1}^n {a_i f_i } } \right\| \leqq C_r \left\| {\sum\limits_{i = 1}^n {a_i e_i } } \right\|$$ We also give a partial uniqueness of unconditional bases under more restrictive conditions.