Synthesis, characterization and Schlenk equilibrium studies of methylmagnesium compounds with O- and N-donor ligands - the unexpected behavior of [MgMeBr(pmdta)] (pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine)

MgMe₂ (1) was found to react with 1,4-diazabicyclo[2.2.2]octane (dabco) in tetrahydrofuran (thf) yielding a binuclear complex [{MgMe₂(thf)}₂(μ-dabco)] (2). Furthermore, from reactions of MgMeBr with diglyme (diethylene glycol dimethyl ether), NEt₃, and tmeda (N,N,N′,N′-tetramethylethylenediamine) in etheral solvents compounds MgMeBr(L), (L = diglyme (5); NEt₃ (6); tmeda (7)) were obtained as highly air- and moisture-sensitive white powders. From a thf solution of 7 crystals of [MgMeBr(thf)(tmeda)] (8) were obtained. Reactions of MgMeBr with pmdta (N,N,N′,N″,N″-pentamethyldiethylenetriamine) in thf resulted in formation of [MgMeBr(pmdta)] (9) in nearly quantitative yield. On the other hand, the same reaction in diethyl ether gave MgMeBr(pmdta) · MgBr₂(pmdta) (10) and [{MgMe₂(pmdta)}₇{MgMeBr(pmdta)}] (11) in 24% and 2% yield, respectively, as well as [MgMe₂(pmdta)] (12) as colorless needle-like crystals in about 26% yield. The synthesized methylmagnesium compounds were characterized by microanalysis and ¹H and ¹³C NMR spectroscopy. The coordination-induced shifts of the ¹H and ¹³C nuclei of the ligands are small; the largest ones were found in the tmeda and pmdta complexes. Single-crystal X-ray diffraction analyses revealed in 2 a tetrahedral environment of the Mg atoms with a bridging dabco ligand and in 8 a trigonal-bipyramidal coordination of the Mg atom. The single-crystal X-ray diffraction analyses of [MgMe₂(pmdta)] (12) and [MgBr₂(pmdta)] (13) showed them to be monomeric with five-coordinate Mg atoms. The square-pyramidal coordination polyhedra are built up of three N and two C atoms in 12 and three N and two Br atoms in 13. The apical positions are occupied by methyl and bromo ligands, respectively. Temperature-dependent ¹H NMR spectroscopic measurements (from 27 to −80 °C) of methylmagnesium bromide complexes MgMeBr(L) (L = thf (4); diglyme (5); NEt₃ (6); tmeda (7)) in thf-d₈ solutions indicated that the deeper the temperature the more the Schlenk equilibria are shifted to the dimethylmagnesium/dibromomagnesium species. Furthermore, at −80 °C the dimethylmagnesium compounds are predominant in the solutions of Grignard compounds 4-6 whereas in the case of the tmeda complex7 the equilibrium constant was roughly estimated to be 0.25. In contrast, [MgMeBr(pmdta)] (9) in thf-d₈ revealed no dismutation into [MgMe₂(pmdta)] (12) and [MgBr₂(pmdta)] (13) even up to −100 °C. In accordance with this unexpected behavior, 1:1 mixtures of 12 and 13 were found to react in thf at room temperature yielding quantitatively the corresponding Grignard compound 9. Moreover, the structures of [MgMeBr(pmdta)] (9c), [MgMe₂(pmdta)] (12c), and [MgBr₂(pmdta)] (13c) were calculated on the DFT level of theory. The calculated structures 12c and 13c are in a good agreement with the experimentally observed structures 12 and 13. The equilibrium constant of the Schlenk equilibrium (2 9c ? 12c + 13c) was calculated to be K_gas = 2.0 × 10⁻³ (298 K) in the gas phase. Considering the solvent effects of both thf and diethyl ether using a polarized continuum model (PCM) the corresponding equilibrium constants were calculated to be K_thf = 1.2 × 10⁻³ and K_ether = 3.2 × 10⁻³ (298 K), respectively.     

Selective kinetic spectrophotometric method for determination of gatifloxacin based on formation of its N-vinyl chlorobenzoquinone derivative

A selective and simple kinetic spectrophotometric has been developed, for the first time, for the determination of gatifloxacin (GAT) in its dosage forms. The method was based on the formation of a colored N-vinyl chlorobenzoquinone derivative of GAT by its reaction with 2,3,5,6-tetrachloro-1,4-benzoquinone in presence of acetaldehyde. The formation of the colored product was monitored spectrophotometrically by measuring the absorbances at 655 nm. The factors affecting the reaction were studied and optimized. The stoichiometry of the reaction was determined, and the reaction pathway was postulated. Under the optimized conditions, the initial rate and fixed time (at 5 min) methods were utilized for constructing the calibration graphs. The graphs were linear in the concentration ranges of 2–100 and 10–140 μg ml^?1 with limits of detection of 0.84 and 3.5 μg ml^?1 for the initial rate and fixed time methods, respectively. The analytical performance of both methods was fully validated, and the results were satisfactory. The proposed methods were successfully applied to the determination of GAT in its commercial dosage forms. The label claim percentages were 99.7–100.5 and 98.2–99.5% for the initial rate and fixed time methods, respectively. Statistical comparison of the results with those of the reference method showed excellent agreement and proved that there was no significant difference in the accuracy and precision between the reference and the proposed methods. The proposed methods are superior to all the previously reported spectrophotometric methods in terms of the procedure simplicity and assay selectivity.     

On total covers of graphs

A total cover of a graph G is a subset of V(G)E(G) which covers all elements of V(G)E(G). The total covering number ₂(G) of a graph G is the minimum cardinality of a total cover in G. In [1], it is proven that ₂(G)[n/2] for a connected graph G of order n. Here we consider the extremal case and give some properties of connected graphs which have a total covering number [n/2]. We prove that such a graph with even order has a 1-factor and such a graph with odd order is factor-critical.     

Umlagerungen von Heterocyclen,IX Mesoionische Sechsringheterocyclen,XV Ketenoide Umlagerungen mesoionischer Pyrimido [1,2-a]chinoline

Tricyclic pyrimidine betaines2, which are obtained from the reaction of 2-anilino quinolines (4) and 2,4,6-trichlorophenyl malonates (3) rearrange at temperatures above 200°Cvia ketene intermediates. Formation of either the ketene11 or the acylketene16 depends upon the reaction medium (2,4,6-trichlorophenol or diphenyl ether as solvent). The structures of the resulting rearranged products6 or7, resp., were established in the case of the pyrimido[3,4-a]quinoline7 by an independent synthesis, and for the 4-hydroxy-2-quinolone6 by degradation to the quinazolone19.     

Bonding corneal tissue: applications of photoactivated diazopyruvoyl cross-linking agent

Photoactivated bis-diazopyruvamide-N,N'-bis(3-diazopyruvoyl)-2,2'-(ethylenedioxy)bis-(ethylamine), (DPD)-was previously shown to bond materials containing type I collagen. However, tensile strength of bonded collagenous tissue ( approximately 78% water) was low compared with that of dehydrated collagenous gelatin ( approximately 14% water). Here we investigated the role of water in corneal tissue bond strength and in bonding corneal tissue to glass. Bonding corneal tissue to glass may be of value in surgically anchoring keratoprostheses to corneas to alleviate problems with extrusion. Bovine corneal samples were lyophilized for various times resulting in tissue hydrations of zero (no water content) to approximately 3.7 (normal water content). The lyophilized corneal tissue was bonded to solid gelatin sheets, to other corneal samples and to glass using 0.3M DPD in chloroform. Control runs used chloroform only. Samples were irradiated with 100 or 200 J of 320-500 nm light. Strong bonds formed with all three materials when corneal tissue hydration was 1. No bonding occurred with chloroform alone. Formation of strong bonds only occurs with hydration levels 相似文献   

A redetermination of the lifetime of the 4s 5s (3S1) level in Ca by high-rate electron—photon stepwise pulse excitation

The radiative lifetime of the 4s 5s (³S₁) level in Ca was measured using two-step excitation of atoms in a beam which traverses a cold-cathode Penning discharge, where, by electron impact the atoms are excited to the metastable 4s 5p (³P_{2, 1, 0}) states. Immediately thereafter, the beam is crossed with a pulse-modulated cw dye laser beam to populate the final state selectively. Using a pulse-modulation frequency of 0.5 MHz, a preliminary value of 12.4 ± 0.5 ns was obtained with a statistical error of 0.4%. The wide limits of systematic error reflect an assumed uncertainty in the excitation function and possible distortion in the fluorescence decay requiring further study.     

Preparation and IR-spectroscopic study of charge transfer complexes of naphthalene derivatives with some tri- and di-nitrobenzenes

The charge transfer complexes of naphthalene and some of its derivatives with some trinitro- and dinitrobenzenes are prepared and investigated by irspectroscopy. The shifts in the bands due to functional groups as well as the _CH bands of both donor and acceptor are found to be indicative for the type of bonding in the charge transfer complex.

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Darstellung und IR-spektroskopische Untersuchungen an Charge Transfer Komplexen von Naphthalinderivaten mit Di- und Tri-nitrobenzolen

Zusammenfassung Aus den Verschiebungen der Bandenlagen bei der Komplexierung, bzw. aus der Abhängigkeit der Bandenlagen von den funktionellen Gruppen, wird der Bindungstyp der Charge-Transfer-Komplexe ermittelt.