Chlorodiazaphospholines as intermediates in the synthesis of 1,2-dihydro-2-alkenyl-3H-pyrazol-3-ones and 2-pyrrolylacetates

New derivatives of 1,2-dihydro-2-alkenyl-3H-pyrazol-3-ones 6 and 7 have been synthesized at room temperature by a one-pot two-step reaction of PCl₃, a ketone methylhydrazone, and a β -keto ester. With ketone methylhydrazones bearing at least a phenyl group in the α -positions to the CN bond and in the second step β -keto esters, such as propionyl- or butyrylacetates, we obtained 2-pyrrolylacetates 8 as unexpected products together with pyrazolones 7 . The ratio of the two products depends on the nature of the groups in the α -positon to the CN bond. A chlorodiazaphospholine 1 is the key intermediate of this new reaction, and a plausible mechanism of formation of the azaheterocycles is reported.     

Longitudinal vibrations of pre-twisted bars with “asymmetric” boundary conditions

Summary In a previous paper concerning the determination of angular frequencies of a twisted straigth bar of constant section, only three simple constraint conditions at the ends had been considered (free end, constrained end). In the present paper the other seven possible (asymmetric) constraint conditions are considered and the corresponding frequency equations are found. A final numerical example with several increasing twisting degrees shows the different influence of this increase upon the frequencies having axial or torsional origin.

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Sommario In un precedente lavoro le equazioni di equilibrio dinamico di un'asta svergolata soggetta a vibrazioni libere lungo il proprio asse erano state risolte in forma chiusa per tre sole condizioni di vincolo al contorno particolarmente semplici (estremità torsionalmente ed assialmente libere o incastrate). Nel presente lavoro vengono determinate le formule finali relative alle altre sette condizioni di vincolo che si ottengono imponendo in almeno una delle estremità dell'asta la rotazione libera e lo spostamento assiale impedito o viceversa. Viene anche svolto un esempio di calcolo numerico determinando in uno dei casi considerati il modo di variare delle prime pulsazioni proprie al crescere dello svergolamento dell'asta.

     

A new approach to Cullen-regular functions of a quaternionic variable

In this Note we announce the basic elements and results of a new theory of regular functions of one quaternionic variable. The theory we describe follows an idea of Cullen, but we use a more geometric approach to show that it is possible to build a rather complete theory. To cite this article: G. Gentili, D.C. Struppa, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Uniformities of Fréchet-Nikodym Type on Vitali Spaces

Vitali spaces are a simultaneous generalization of Riesz spaces, Boolean rings, MV-algebras. We study uniformities on Vitali spaces which make lattice operations, partial sum and subtraction uniformly continuous, proving that every such uniformity is generated by its 0-neighbourhood system. This result is not true in general for lattice uniformities on lattices. As consequence we obtain general decomposition theorems for exhaustive and locally exhaustive group-valued measures and decompositions of Lebesgue and Hewitt-Yosida type.     

Wittig Reaction: Role of Steric Effects in Explaining the Prevalent Formation of Z Olefin from Nonstabilized Ylides

Abstract

For understanding the mechanism involved in the Wittig reaction, it is important to know the factors which influence the stability of 1,2-oxaphosphetane intermediates with pentacoordinate phosphorus; in these intermediates, the steric factor plays a predominant role. Studying the Wittig reaction between nonstabilized ylides and different aldehydes, we noted that the stereochemical outcome driving toward Z-olefin formation was influenced only by different steric factors. The proposed mechanism differs from those previously reported because it underlines the fundamental role of the two cis/trans oxaphosphetane intermediates with the oxygen atom in equatorial position.     

A Fast Catalytic Process of Transfer of a Phosphorus Atom: How Folding of the Reagent is Related to its Catalytic Activity. A Possible Correlation with Rna Behavior

Abstract

A simple and very fast process of transfer of a phosphorus atom, performed by a simple molecule acting as catalyst in an almost infinite catalytic cycle is described. The catalyst donates a P atom to a mixture of two different Grignard reagents giving, in a very fast and in a highly selective manner, only one phosphorus-containing compound with an enormous rate enhancement with respect to the corresponding no-catalyzed reaction which gives a final cluttered mixture of many organophosphorus products. The focal factor to explain this highly selective process of P transport lies in the folded structure of the reagent with particular angles around the phosphorus atom which can facilitate the formation of cyclic trigonal bipyramidal pentacoordinated species and then its catalytic activity. In a similar manner, RNA can adopt, in a precise position, a particular three-dimensional structure that might facilitate the formation of pentacoordinated species leading to the catalytic function.     

One-electron bonds in copper–aluminum and copper–gallium complexes

Odd-electron bonds have unique electronic structures and are often encountered as transiently stable, homonuclear species. In this study, a pair of copper complexes supported by Group 13 metalloligands, M[N((o-C₆H₄)NCH₂PⁱPr₂)₃] (M = Al or Ga), featuring two-center/one-electron (2c/1e) σ-bonds were synthesized by one-electron reduction of the corresponding Cu(i) ⇢ M(III) counterparts. The copper bimetallic complexes were investigated by X-ray diffraction, cyclic voltammetry, electron paramagnetic spectroscopy, and density functional theory calculations. The combined experimental and theoretical data corroborate that the unpaired spin is delocalized across Cu, M, and ancillary atoms, and the singly occupied molecular orbital (SOMO) corresponds to a σ-(Cu–M) bond involving the Cu 4p_z and M ns/np_z atomic orbitals. Collectively, the data suggest the covalent nature of these interactions, which represent the first examples of odd-electron σ-bonds for the heavier Group 13 elements Al and Ga.

Hanging on by a thread. Formally zerovalent copper complexes with an Al(iii) or Ga(iii) support were investigated. The combined experimental and theoretical data corroborate the presence of an odd-electron σ-bond between Cu and the Group 13 center.

Odd-electron σ-bonds, where the electrons are delocalized between two atoms, can occur as two-center/one-electron (2c/1e) or two-center/three-electron (2c/3e) interactions. Proposed by Pauling in 1931,¹ odd-electron σ-bonds have garnered attention because of their fundamental importance to chemical bonding and their relationship to radical species generated during oxidative stress in biological systems.^2–14 Examples of compounds exhibiting odd-electron bonding are typically homonuclear (like H₂⁺, He₂⁺, and alkali metal dimers) and transiently stable, limiting them to spectroscopic characterization.^1,11,15–18The first solid-state structure of a formally one-electron σ-bond was a tetraphosphabenzene species (Fig. 1a) which was formed by the coupling of two diphosphirenyl radicals.¹⁹ Following this discovery, the formation of discrete 2c/1e σ-bonds, where the odd-electron is delocalized between two homonuclear main group centers, was reported for B·B and then extended to P·P.^8,17,20 Of note, the first solid-state structure of a B·B compound was reported in only 2014 (Fig. 1b).²¹ Examples of 2c/1e σ-bonds between the heavier Group 13 congeners are even more lacking because of the greater propensity for their unpaired spins to couple, forming larger more stable clusters.⁸ To our knowledge, there are only three structurally characterized examples of odd-electron bonds for the heavy Group 13 atoms,²² and these examples are all homonuclear π-radicals (Fig. 1c).^23–26Open in a separate windowFig. 1Select examples of structurally characterized molecules (a–d) featuring odd-electron bonds.Heteronuclear odd-electron σ-bonds are also rare. The Cu(TPB) complex, where TPB is a trisphosphinoborane, is the single structural example of a 2c/1e bond between heteroatoms (Fig. 1d).²⁷ The authors described the bonding as Cu·B, where the unpaired electron is heavily polarized toward B. A theoretical study predicted that such a bond would also exist between Cu and Al, but no heavier analogues of Cu(TPB) have been synthesized to date.²⁸ Furthermore, the heavier Group 13 elements by virtue of their lower electronegativity compared to B should facilitate greater covalent interactions with the Cu center.Hence, we sought to target formally zerovalent Cu complexes supported by Al(III) or Ga(III) as an extension of the previously reported isoelectronic nickelate species and Cu(TPB).²⁹ Herein, we describe the synthesis, structure, spectroscopic characterization, and DFT calculations of cationic [CuML]⁺ complexes (L = [N((o-C₆H₄)NCH₂PⁱPr₂)₃]³⁻; M = Al and Ga) as well as their one-electron reduced metalloradical counterparts that feature discrete 2c/1e bonds.