Synthesis and spectroscopic features of bis(tetramethylammonium) and bis(benzyltriethylammonium) salts possessing a μ-oxo-bis(trichloroferrate) anion structure

Summary The two -oxo-bis(trichloroferrate) salts (1) and (3) with diamagnetic ammonium cations are prepared as prototype compounds possessing an oxo-bridged dimer anion structure in which each iron(III) centre coordinates tetrahedrally to the three Cl ligands in addition to the bridging ligand. Antiferromagnetic coupling between the two iron centres in the anion complex is indicated by the low room-temperature effective magnetic moments (1.71–1.74 _B). The i.r. and electronic absorption spectra are in accord with the proposed anionic oxygen bridge structure.     

Organotin Dyes: Synthesis and Structural Characterization of Dibutyltin and Dimethyltin Complexes with 2, 2′‐Dihydroxyazobenzene

The preparation and structures of 2, 2′‐dihydroxyazobenzenato‐dibutyl‐tin [Bu₂SnL] and 2, 2′‐dihydroxyazobenzenato‐dimethyl‐tin [Me₂SnL] are described. The complexes were characterized by IR, NMR (¹H, ¹³C, ¹¹⁹Sn) and UV/VIS spectra. The crystal structures were determined by X‐ray diffraction on single crystals. [Bu₂SnL]: monoclinic, space group P2₁/c, cell constants at 208 K: a = 860.73(5), b = 973, 51(18), c = 2340.0(3) pm, β = 93.615(11)°; R₁ = 0.0546. [Me₂SnL]: orthorhombic, space group Pbcn, cell constants at 208 K: a = 1914.6(4), b = 1041.3(3), c = 1323.27(14) pm; R₁ = 0.0529.     

Novel unsymmetrical PCP′ pincer ligands and their palladium(II) complexes

Synthetic routes towards novel PCP′ pincer ligands were devised. Ligand 1-(Pr₂ⁱPOCH₂)-3-(Bu₂^tPCH₂)(C₆H₄) is prepared in a three step synthesis from 1,3-benzenedimethanol and 1-(Pr₂ⁱPO)-3-(Bu₂^tPCH₂)(C₆H₄) is accessible in three steps from 3-hydroxybenzylalcohol. Both their palladium(II) complexes are prepared in good yields but are distinctly different since [PdCl{(C₆H₃)(OPPr₂ⁱ)-2-(CH₂PBu₂^t)-6}] possesses two five-membered palladacycles, whereas [PdCl{(C₆H₃)(CH₂PBu₂^t)-2-(CH₂OPPr₂ⁱ)-6}] is unusual for a pincer complex in that it contains both five- and six-membered palladacycles. Both compounds also represent the first examples of pincer complexes where one donor is a phosphinite and the other is a phosphine. The X-ray structures of these complexes were solved and are discussed. The data reveal that an increase in the metallacycle ring-size leads to changes in bond lengths, but more importantly to significant increases in the bond angles.     

Characterizing moore groups by tensor products of irreducible representations

It is shown that all irreducible representations of a σ-compact Lie group G have to be finite dimensional provided that for every π in the reduced dual of G the tensor product π ? \(\bar \pi \) has a discrete support.     

13C Spin-Lattice Relaxation Times and the Mobility of Organic Molecules in Solution

While the chemical shifts and coupling constants of ¹³C NMR belong to the most powerful tools available to the organic chemist for the solution of structural problems, increasing interest is being shown in ¹³C spin-lattice relaxation times T₁ as structural parameters. Together with the nuclear Overhauser effects arising by proton decoupling of ¹³C NMR spectra, the T₁ values of ¹³C nuclei in a molecule permit conclusions to be drawn with regard to relaxation mechanisms. They reflect the inter- and intramolecular mobility of a molecule, and thus complement the results of temperature-dependent NMR spectroscopy. The T₁ differences within a molecule show, for instance, whether the molecular motion is anisotropic in solution, whether the internal motion of groups is subject to steric hindrance, the extent to which strong intermolecular or interionic interactions affect the flexibility of the molecule, and which parts of the molecule are rigid and which are flexible. Finally, differences between the T₁ values measured for the ¹³C nuclei of a molecule frequently provide a reliable aid in the assignment of ¹³C NMR spectra, particularly in cases of signal crowding and multiplet overlapping.     

PHYTOCHROME MACRO-DISTRIBUTION, LOCAL PHOTOCONVERSION AND INTERNAL PHOTON FLUENCE RATE FOR Cucurbita pepo L. COTYLEDONS

Abstract— Using 7-day-oId cotyledons of Cucurbita pepo L., local phytochrome photoconversions could be measured for blue, red and far-red light. For this purpose, after nonsaturating irradiation, cotyledons were sliced into discs 0.3 to 0.5 mm thick and signals measured. This method also yielded the internal phytochrome distribution of the cotyledons with maximal concentration near the adaxial surface, dropping to about 50% in the center and reaching again about 90% at the abaxial surface. Local phytochrome conversion rates were used to calculate internal fluence rates across the cotyledons. Relative internal fluence rates were also derived from measured reflectances and transmittance according to the Kubelka-Munk theory. The general shape of the internal fluence distribution calculated on the basis of these two methods coincided well. It was observed that the internal local photoconversion is proportional to the penetration depth over a wide range of incident fluences and for all wavelengths tested, showing in addition that reciprocity holds. A method to calculate internal fluence rates by a simplified procedure assuming either linear or exponential functions is described.     

The central role of the metal ion for photoactivity: Zn– vs. Ni–Mabiq

Photoredox catalysts are integral components of artificial photosystems, and have recently emerged as powerful tools for catalysing numerous organic reactions. However, the development of inexpensive and efficient earth-abundant photoredox catalysts remains a challenge. We here present the photochemical and photophysical properties of a Ni–Mabiq catalyst ([Ni^II(Mabiq)]OTf (1); Mabiq = 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2-biquinazolino)-[15]-1,3,5,8,10,14-hexaene1,3,7,9,11,14-N₆)—and of a Zn-containing analogue ([Zn^II(Mabiq)OTf] (2))—using steady state and time resolved optical spectroscopy, time-dependent density functional theory (TDDFT) calculations, and reactivity studies. The Ni and Zn complexes exhibit similar absorption spectra, but markedly different photochemical properties. These differences arise because the excited states of 2 are ligand-localized, whereas metal-centered states account for the photoactivity of 1. The distinct properties of the Ni and Zn complexes are manifest in their behavior in the photo-driven aza-Henry reaction and oxidative coupling of methoxybenzylamine.

The development of earth-abundant photoredox catalysts remains a challenge. Studies of Ni- and Zn-Mabiq complexes demonstrate how the coordinating metal ion influences the photochemistry, photodynamics and reactivity of photocatalysts.     

Gas chromatographic determination of aromatic amines in water samples after solid-phase extraction and derivatization with iodine II. Enrichment

A procedure for the enrichment of aromatic amines via solid-phase extraction was developed. A HR-P phase based on styrene–divinylbenzene was used for the investigations, generally followed by derivatization with iodine and determination via GC–ECD. The recoveries of 53 aromatic amines in a drinking water matrix at pH 9 were determined. Most anilines showed relative recoveries between 80–120% with relative standard deviations of ≤5% at concentration levels between 10 and 20 μg l⁻¹. The comparison with a wastewater matrix led to similar results. The enrichment procedure was applied to real samples, e.g., samples of ammunition wastewater.     

Heterocyclen aus α-nitroolefinen. XII . 3-Acetyl-4,5-dihydro-5-(methylenamino)furane und 3-acylpyrrole aus α-nitroolefinen und β-diketonen

From α-nitroolefines 1 and β-diketones 2 3-acetyl4,5-dihydro-5-(methy1eneamino)furans 5 are prepared. Furans 5 react in acid medium to yield 1-unsubstituted 3-acylpyrroles 6 , catalytic hydrogenation yields 1-substituted 3-acylpyrroles 9 . The ¹H-nmr and ¹³C-nmr investigations prove the constitutions.     

Metallorganische diazoalkane : XVI. Synthese von silyldiazoalkanen Me3Si(LnM)CN2

Silyldiazoalkanes Me₃Si(L_nM)CN₂ (L_nM = Me₃Si, Me₃Ge, Me₃Sn, Me₃Pb; Me₃As, Me₃Sb, Me₃Bi) have been synthesized by three different routes: (a) reactions of the Me₃SiCHN₂ with metal amides L_nMNR¹R² of Group IVB and VB elements, using Me₃SnCl as catalyst; (b) reactions of the in situ prepared organolithium compound Me₃SiC(Li)N₂ with organometallic chlorides Me₃MCl (M = Si, Ge); (c) tincarbon bond cleavage reaction of (Me₃Sn)₂CN₂ with Me₃SiN₃, affording Me₃SnN₃, traces of bis(trimethylsilyl)diazomethane (Me₃Si)CN₂, trimethylsilyl(trimethylstannyl)diazomethane Me₃Si(Me₃Sn)CN₂ and bis(trimethylsilyl)aminoisocyanide (Me₃Si)₂NNC as the major reaction products. IR and NMR data (¹H, ¹³C, ²⁹Si, ¹¹⁹Sn, ²⁰⁷Pb) of the new heterometal-diazoalkanes are reported and discussed in comparison to relevant compounds of the organometallic diazoalkane series.