Adsorption of di-2-pyridyl ketone salicyloylhydrazone on silica gel: characteristics and isotherms

The adsorption of DPKSH onto silica gel was investigated, at 25±1 °C and pH 1, 4.7 and 12. For the same DPKSH concentration interval, the minimum required time of contact for adsorption maximum at pH 4.7 was smaller than at pH 1 and the maximum amount of DPKSH adsorbed per gram of silica at pH 1 is smaller than at pH 4.7. At pH 12 the DPKSH adsorption onto silica gel was not significant. The adsorption data followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The maximum amount of solute adsorbed (m_ads^max) and the adsorption constant, K_L, were derived from Langmuir isotherm. The Freundlich constants 1/n and K_F related, respectively, to the energetic heterogeneity of adsorption sites and an empirical constant were evaluated. The mean sorption free energy (E) of DPKSH adsorption onto silica gel was calculated from D-R isotherm indicating a physical adsorption mode. Finally, conductimetric titrations showed the silica particle basicity and acidity as 0.002 and 0.3 mmol g⁻¹, respectively.     

The first pyridyl N,N′-coordinated di-2-pyridyl ketone oxime,fac-tricarbonylchloro(di-2-pyridyl ketone oxime)rhenium(I) dimethyl sulfoxide solvate

The structure of the first metal compound of pyridyl N,N′-coordinated di-2-pyridyl ketone oxime (dpk-o), fac-tri­carbonyl­chloro­(di-2-pyridyl-κN ketone oxime)­rhenium(I) di­methyl sulfoxide solvate, [ReCl(C₁₁H₉N₂O)(CO)₃]·C₂H₆OS, (I), is reported. The coordinated atoms (two N atoms from the pyridyl rings, three C atoms from the carbonyl groups and one Cl atom) are in a distorted octahedral arrangement, with the major distortion being due to the constraints associated with the binding of dpk-o. The packing of the mol­ecules shows antiparallel tapes of (I), with a network of classical (O⃛H—O) and non-classical (O⃛H—C) hydrogen bonds between the di­methyl sulfoxide solvate molecule and the complexed metal moiety.     

Optosensing properties of fac-Re(CO)(3)(dpknph)Cl (dpknph=di-2-pyridyl ketone p-nitrophenyl hydrazone)

Optical and thermodynamic measurements on fac-Re(CO)(3)(dpknph)Cl in polar non aqueous solvents revealed the existence of two interlocked conformational forms for fac-Re(CO)(3)(dpknph)Cl. The equilibrium distribution of the low (alpha-) and high (beta-) energy conformations is solvent dependent, controlled by the dipole moment of the solvent molecules and their orientation around the total dipole of fac-Re(CO)(3)(dpknph)Cl. The interplay between the alpha- and beta-conformations of fac-Re(CO)(3)(dpknph)Cl, allowed calculations of their extinction coefficients, by forcing the equilibrium to shift to one conformation, using chemical stimuli. In DMSO and DMF extinction coefficients of 87 000+/-2000 and 35 000+/-2000 M(-1) cm(-1) were calculated for the beta- and alpha-conformations of fac-Re(CO)(3)(dpknph)Cl at lambda(max.), respectively. Thermo-optical measurements on fac-Re(CO)(3)(dpknph)Cl, allowed calculations of the activation parameters for the interconversion between the alpha- and beta-conformations of fac-Re(CO)(3)(dpknph)Cl. In DMSO and DMF changes in enthalpy (DeltaH(?)) of -11.2+/-1.3 and 10.9+/-0.5 kJmol(-1), entropy (DeltaS(?)) of -12.7+/-4.3 and 29.4+/-1.7 JK(-1) mol(-1), and free energy (DeltaG(?)) of -7.5+/-0.2 and+2.2+/-0.2 kJmol(-1) and hence equilibrium constants of 20.9+/-1.7 and 0.4+/-0.1 were calculated for fac-Re(CO)(3)(dpknph) at 295 K. The high values for the extinction coefficients and low values for the activation parameters for the interconversion between the alpha- and beta-conformations of fac-Re(CO)(3)(dpknph)Cl, in polar non aqueous solvents allowed the use of these systems as molecular sensors to probe their structural relaxation and interactions with their surroundings. These systems (fac-Re(CO)(3)(dpknph)Cl and surrounding solvent molecules) optically sense chemical and physical stimuli and their sensing power depends on the intensity and nature of these stimuli, i.e. the systems exhibit a high degree of sensitivity and selectivity.     

Synthesis and herbicidal activities of a series of di(aminopyrazoly) ketone derivatives

In order to obtain new lead compounds with high herbicidal activity, a series of 5‐amino pyrazole derivatives were designed and synthesized using a series of relational synthons. Their structures were determined by IR, ¹H NMR, and elemental analyses. These compounds were screened for herbicidal activities against rape and barnyard grass. Their structure‐activity relationships are discussed.     

Structural and spectral studies of di-2-pyridyl ketone 3-piperidyl- and 3-hexamethyleneiminylthiosemicarbazone and their cobalt(II), nickel(II) and copper(II) complexes

Cobalt(II), nickel(II) and copper(II) complexes of di-2-pyridyl ketone 3-piperidyl- and 3-hexamethyleneiminyl-thiosemicarbazones (HDPypip and HDPyhexim, respectively) have been prepared and characterized by physical and spectral methods. Use of 1:2 thiosemicarbazone-to-metal chloride molar ratios in the preparation of the complexes has produced both mononuclear and polynuclear species for the three metal ions. Crystal structures of the HDPypip, HDPyhexim and [Ni(DPyhexim)Cl] have been determined and aid the assignments of the i.r., n.m.r., u.v.–vis. n.i.r. and e.s.r. spectra for the various complexes.     

Claisen-Umlagerung von 2-Propinyl-(3-pyridyl)-und Allyl-(3-pyridyl)äthern

Claisen Rearrangement of 2-Propinyl (3-Pyridyl) and Allyl (3-Pyridyl) Ethers

1 Verbindungen vom Typ 1 werden mit Ausnahme von 17 und 25 als Äther benannt. Der systematische Name von 1 ist: 3-(2-Propinyl)oxy-pyridin.

2-Propinyl (3-pyridyl) ether ( 1 ), synthesized from the corresponding 3-pyridinol, was heated in DMF or decane at 208° in a sealed tube. In this way the furopyridines 2 and 3 were formed, and furthermore the pyranopyridine 4 if decane was used as solvent (Scheme 1). The same reactions took place with (2-methyl-3-pyridyl) 2-propinyl ether ( 14 ). In DMF only 15 , and in decane 16 as well as 15 were formed (Scheme 3). The rearrangement of the pyridine derivative 17 , which is substituted in both O-positions to the ether moiety, gave in both DMF and decane the diastereoisomeric tetracyclic compounds 18 and 19 . The same kind of reaction took place with 25 (Scheme 4). In the thermolysis of the allyl 3-pyridyl ether ( 27 ) cyclization was observed, too. The isolated product has the structure of the dihydrofuropyridine 28 (Scheme 6). The substituted allyl 3-pyridyl ether 30 reacted in the same way to the dihydrofuropyridine 31 (Scheme 6).     

Molybdenum- and tungsten(II) monometallic 3-(2-pyridyl)pyrazole and bimetallic 3-(2-pyridyl)pyrazolate complexes

Molybdenum and tungsten complexes containing the pypzH (3-(2-pyridyl)pyrazole) ligand as a chelating bidentate are prepared: [Mo(CO)(4)(pypzH)], cis-[MoBr(η(3)-allyl)(CO)(2)(pypzH)], cis-[MoCl(η(3)-methallyl)(CO)(2)(pypzH)], [MI(2)(CO)(3)(pypzH)] (M = Mo, W) from [Mo(CO)(4)(NBD)] or the adequate bis(acetonitrile) complexes. The deprotonation of the molybdenum allyl or methallyl complexes affords the bimetallic complexes [cis-{Mo(η(3)-allyl)(CO)(2)(μ(2)-pypz)}](2) or [cis-{Mo(η(3)-methallyl)(CO)(2)(μ(2)-pypz)}](2) (μ(2)-pypz = μ(2)-3-(2-pyridyl-κ(1)N)pyrazolate-2κ(1)N). The allyl complex was subjected to an electrochemical study, which shows a marked connection between both metallic centres through the bridging pyridylpyrazolates.     

Heterocyclization of cycloalkenes with di(2-pyridyl) diselenide in the presence of antimony pentachloride

Cycloalkenes react with di(2-pyridyl) diselenide in the presence of antimony pentachloride with the formation of products of the selenenylating electrophile cycloaddition at the multiple bond. The final products of heterocyclization, chloroantimonates(III) of 2,3-dihydro[1,3]selenazolo[3,2-a]pyridinium derivatives were isolated.     

Electronic emission and absorption spectroscopy of the rhenium complexes Re(CO)3Cl(phosphine)2

Summary The compounds Re(CO)₃Cl(L)₂,L=triphenylphosphine, tri-p-tolyphosphine, and Re(CO)₃-Cl(L),L=1,2-bis(diethylphosphinoethane) are luminescent in solution and in crystalline form when excited between 351 nm and 514 nm at temperatures ranging from 10 K to room temperature. The absorption spectra contain a weak (E 10M ^–1 cm^–1) band in the visible region of the spectrum between 400 and 500 nm. The lowest energy transition giving rise to these spectroscopic features is assigned to a d-d transition.

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Elektronenemissions- und Absorptionsspektroskopie der Rheniumkomplexe Re(CO)₃Cl(Phoshin)₂

Zusammenfassung Die Verbindungen Re(CO)₃Cl(L)₂ mitL=Triphenylphosphin, Tri-p-tolylphosphin und Re(CO)₃Cl(L)₂ mitL=1,2-Bis(diethylphosphinoethan) sind in Lösung und im kristallinen Zustand bei Anregung zwischen 351 und 514 nm im Temperaturbereich von 10 K bis Raumtemperatur lumineszent. Die Absorptionsspektren enthalten im sichtbaren Bereich zwischen 400 und 500 nm eine schwache Bande von 10M ^–1 cm^–1. Der energetisch tiefstliegende Übergang, der für dieses Verhalten verantwortlich ist, wird einem d-d-Übergang zugeordnet.

     

Cycloaddition of di(2-pyridyl) diselenide to styrene activated with antimony pentachloride

A reaction of styrene with the di(2-pyridyl) diselenide??antimony pentachloride system furnishes 2,3-dihydro[1,3]selenazolo[3,2-a]pyridinium chloroantimonates(III) and (V), the products of cycloaddition of the selenylating agent at the multiple bond.     

Theoretical studies of magnetic interactions in Mn(II)(hfac)(2)[di(4-pyridyl)phenylcarbene] and Cu(II)(hfac)(2)[di(4-pyridyl)phenylcarbene].

Bis(hexafluoroacetylacetonato(hfac))manganese(II) coordinated with di(4-pyridyl)phenylcarbene, Mn(II)(hfac)(2)[di(4-pyridyl)phenylcarbene] (1a) and its copper analogue Cu(II)(hfac)(2)[di(4-pyridyl)phenylcarbene] (2a) have attracted great interest from the viewpoint of photoinduced magnetism. The complexes 1a and 2a are regarded as the new d-pi-p conjugated systems containing transition metal ion and carbene as spin sources. The magnetic measurements demonstrated antiferromagnetic and ferromagnetic effective exchange interactions for 1a and 2a, respectively. Here, we have performed UHF and UHF plus DFT hybrid calculations (UB3LYP) to elucidate the nature of the through-bond effective exchange interaction between Mn(II) (or Cu(II)) ion and triplet carbene sites in 1a (or 2a) and their model complexes. The natural orbital analysis of the UHF and UB3LYP solutions and CASCI calculations for the simplest models of 1a and 2a are performed to elucidate relative contributions of spin polarization (SP) and spin delocalization (SD) (or superexchange (SE)) interactions for determination of the sign of J(ab) values. Mn(II) carbene complex 1a shows an antiferromagnetic interaction because of the pi-type antiferromagnetic SE effect and the pi-type SP effect, while the positive J(ab) value for Cu(II) carbene complex 2a can be explained by the fact that ferromagnetic SE and SP interactions due to orbital orthogonality are more effective than the sigma-type antiferromagnetic SE interaction. The ligand coordination effects of both 4-pyridylcarbene and hfac play crucial roles for determination of the J(ab) values, but the ligand coordination effect of hfac is more important for the active control of charge or spin density distributions than that of 4-pyridylcarbene. The spin alignment mechanisms of 1a and 2a are indeed consistent with SE plus SP rule, which is confirmed with the shape and symmetry of natural orbitals, together with charge and spin density distributions.