Reactions of nickel(II) 2,21-dimethyl-2-aza-21-carbaporphyrin with phenyl Grignard reagents, phenyllithium, and n-butyllithium

Addition of a phenyl Grignard reagent to a toluene solution of the nickel(II) chloride complex of a dimethylated inverted porphyrin, (2-NCH3-21-CH3CTPP)NiIICl (1), at 203 K results in the formation of a rare paramagnetic (sigma-phenyl)nickel(II) species, (2-NCH3-21-CH3CTPP)NiIIPh (2). The coordination of the sigma-phenyl in 2 is determined by a unique pattern of three sigma-phenyl resonances (ortho 375.0 ppm; meta 108.94 ppm; para 35.68 ppm (at 283 K)) in the 1H NMR and 2H NMR spectra. The (sigma-phenyl)nickel(II) compound 2 is in the high-spin ground electronic state (dxy)2(dxz)2(dyz)2(dz2)1(dx2-y2)1, as confirmed by similarity of the NMR spectra of the equatorial ligand in 1 and 2. Titration of 1 with phenyllithium produces (2-NCH3-21-CH3CTPP)NiIIPh (2). One-electron reduction with excess PhLi yields [(2-NCH3-21-CH3CTPP)NiIIPh]- (3), which can be also generated by independent routes, e.g., by reduction of (2-NCH3-21-CH3CTPP)NiIIPh using lithium triethylborohydride or tetrabutylammonium borohydride. The spectroscopic data indicate that (2-NCH3-21-CH3CTPP)NiIIPh (2) undergoes one-electron reduction without a substantial disruption of the molecular geometry. The presence of two paramagnetic centers in 3, i.e., the high-spin nickel(II) and the carbaporphyrin anion radical, produces remarkable variations in a spectral patterns, such as the upfield and downfield positions of pyrrole resonances (103.78, 96.66, -25.35, -50.97, -92.15, -114.83 ppm (at 253 K)) and sign alternations of the meso-phenyl resonances (ortho -77.81, -79.34 ppm; meta 48.77, 48.04 ppm; para -85.65, -86.46 ppm (at 253 K)). A single species, 4, is detected in the 1H NMR titration of 1 with n-butyllithium. The formation of one- or two-electron-reduced species, [(2-NCH3-21-CH3CTPP)NiBu]- or [(2-NCH3-21-CH3CTPP)NiBu]2-, respectively, is considered to account for the spectroscopic properties of 4 (pyrrole 17.33, 15.45, -5.79, -7.74, -14.62, -58.14 ppm; 21-CH3 3 ppm (at 203 K)). The temperature dependence of the hyperfine shifts of 4 demonstrates pronounced anti-Curie behavior, interpreted in terms of a temperature-dependent spin equilibrium between diamagnetic and paramagnetic states with diamagnetic properties approached as the temperature is lowered. Warming of 2-4 results in complete decomposition via homolytic/heterolytic cleavage of an axial nickel-apical carbon bond. In the case of 2 or 3, the process yields a mixture of two compounds, 5 and 6, which are detected by EPR spectroscopy, demonstrating the anisotropy of the g tensor (5, g1 = 2.237, g2 = 2.092, g3 = 2.090; 6, g1 = 2.115, g2 = 2.030, g3 = 1.940 (in frozen toluene solution at 77 K)).     

Cationic Heteroconjugation Constants in the OHN+ and NHO+ Systems in Propylene Carbonate: Dependence on Difference in Basicity

Cationic heteroconjugation equilibria of more than ninety systems consisting of substituted pyridines, their N-oxides, and trimethylamine N-oxide, i. e., in systems with mixed hydrogen bridges of type OHN⁺ (NHO⁺) were studied in propylene carbonate. Both experimental systems without proton transfer, BH⁺/B₁, and those with proton transfer, B₁H⁺/B, were explored. The stability of the mixed hydrogen bridges, OHN⁺ (NHO⁺), is compared with that of the OHC⁺-type bridges. The influence of the difference in basicity of the conjugate base of the proton donor and the proton acceptor on the presence of the proton transfer equilibria, and, consequently, the possibility of determination of the cationic heteroconjugation constant values is discussed.     

Artin algebras with only preprojective or preinjective modules are of finite type

This work was done while the second author visited Toru. This research was partially supported by the Polish Scientific Grant KBN No. 1222/2/91     

An analysis of mean life and lifetime of unstable elementary particles

A theoretical analysis of the concept of lifetime and mean life of unstable elementary particles is presented. New analytic formulas for lifetime and mean life as a function of decay width and the mass of unstable particle are derived for Breit-Wigner and Matthews-Salam energy distributions. It is demonstrated that, for unstable particles with a larger width or decay energy threshold, the deviation from the generally accepted mean life ^m = ^–1 is significant. The behavior of the decay law P(t) for small times is analyzed, and it is shown that the Breit-Wigner distribution violates the condition P(t = 0) = 0, whereas the Matthews-Salam distribution satisfies it.     

The steric structure of multiflorine methylation products

Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by¹H and¹³C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.

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Die räumliche Struktur von Methylierungsprodukten des Multiflorins

Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (¹H und¹³C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.

     

Europium isotope separation in the HCl/HDEHP extraction system

The^153/151Eu isotope separation factor (q) for the Eu(II)/Eu(III) chemical exchange in the liquid-liquid extraction system, containing Eu (III) in di (2-ethylhexyl) phosphoric acid (HDEHP) and Eu(II) in water acidified with hydrochloric acid, was found to be 0.9993±0.0002 (2) for the single stage. Some theoretical aspects of separation of the Eu isotopes are discussed. The decisive role of the electron exchange reaction and complexation by the counter-ion in the aqueous phase is emphasized.     

Influence of substituents on positron annihilation in styrene copolymers

Results of angular correlation of annihilation radiation (ACAR) and positron annihilation lifetime (PAL) measurements are presented for five styrene copolymers: poly(co-styrene-phenylmaleimide) and its three derivatives with chlorine as well as for one with the OH group substituted at the benzene ring. It occurs that the chlorine substituted at three different positions at the benzene ring poly(co-styrene-o (or-m,-p)-chlorophenylmaleimide) inhibits the formation of the positronium to different extent. The greatest effect is observed in case of the chlorine atom substituted at the benzene ring at the ortho-position towards the nitrogen atom. The two long lifetimes (₃ and ₄) observed in the lifetime spectra are connected with the bimodal distributions of the free volume radius in the samples.     

A definitive method for the determination of trace amounts of cobalt in biological materials by neutron activation analysis

A new, very accurate (definitive) method for the determination of trace amounts of cobalt in biological materials has been devised. The method is based on combination of neutron irradiation with quantitative and selective post-irradiation separation of cobalt from all accompanying radionuclides followed by measurement by -ray spectrometry. Column chromatography in which owing to addition of Co carrier the course of separation can be followed visually is the key element of the separation scheme. Several criteria have been formulated which must be simultaneously fulfilled in order to acknowledge the result as obtained by a definitive method. The high accuracy of the method has been demonstrated by the analysis of several certified reference materials of widely different Co contents.     

Atomic absorption spectrophotometric determination of gold with preconcentration by Donnan dialysis

Donnan dialysis enrichment with tubular cation-exchange membrane was used as a preconcentration method prior to determination of gold by flame atomic absorption spectrometry (FAAS). The value of enrichment factor can be controlled for a particular application through adjustment of the membrane tuning length, dialysis time, carrier flow rate, composition of the receiver solution and by addition of complexing ligand to the receiver or the sample solution. For 10 min dialysis enrichment factor above 3 can be achieved. The detection limit (signal-to-noise ratio = 3) of 35 ng/ml was obtained. RSD at 0.2 mug/ml level was 4.7% (n = 6). The results of dialysis of noble metals mixtures are demonstrated.     

Two-point Padé approximants for formal Stieltjes series

We prove that certain two-point Padé approximants occupying the diagonal of the Padé table form monotone sequences of lower and upper bounds uniformly converging to a Stieltjes function. The results can be applied to the theory of inhomogeneous media for the calculation of the bounds on the effective transport coefficients of heterogeneous materials.