Spectral properties and reactivity of the binuclear complex ion μ-(p-benzoquinonediimine)bis[pentacyanoferrate(II)]

Summary A sodium salt containing the binuclear complex anion -(p-benzoquinonediimine) bis(pentacyanoferrate(II)], [(NC)₅FeHNC₆H₄NHFe(CN)₅]^6- [first described by Herington⁽³⁾) has been isolated as a solid from an oxygenated solution ofp-phenylenediamine and sodium amminepentacyanoferrate(II) in a 12 molar ratio. The i.r. and u.v.-vis. spectra point to a quinonediimine structure for the bridging ligand. In aqueous solution this ion dissociates into aquopentacyanoferrate(II) andp-benzoquinonediiminepentacyanoferrate(II), with k_obs=1.1×10^–2s^–1. The formation of the mononuclear pentacyanoferrate(II) complex of protonatedp-benzoquinonediimine is favoured at pH8. The pK_a value for the coordinated diimine isca. two orders of magnitude higher than that for the free ligand, thus indicating thatp-benzoquinonediimine is stabilized by coordination to the [Fe(CN)₅]^3- moiety, though to a lesser extent than in rutheniumammine analogues.Presented in part at the VIth Argentine Congress on Physical Chemistry, held at Termas de Río Hondo, Santiago del Estero, R. Argentina, April 1989.     

Substituent Effects on Binding Constants of Carotenoids to n-Heptane/AOT Reverse Micelles

The absorption spectra of 6′-apo-β-caroten-6′-ol (1), 6′-apo-β-caroten-6′-oic acid (2), and ethyl 6′-apo-β-caroten-6′-oate (3) were analyzed in homogeneous media and in reversed micelles of AOT (sodium 1,4-bis(2-ethylhexyl) sulfosuccinate) in n-heptane. The possible solute–solvent interactions of these compounds were analyzed in pure solvents by Taft and Kamlet's solvatochromic comparison method. These carotenoids show sensitivity similar to that of medium polarity-polarizability as measured by π*. Moreover, the absorption spectra of carotenoid 3 and to much less extent carotenoid 2 display broadening of the visible bands induced by polar solvents characteristic of carotenoids that contain a carbonyl functional group in conjugation with the carbon–carbon π-electron system. They are also sensitive to the ability of the solvent to accept protons in a hydrogen bond interaction measured by β. This sensitivity follows the expected order: 2>1>3. In the reverse micellar system, while the spectra for 3 remain unchanged, the intensity of the absorption band characteristic of n-heptane for 1 and 2 decreases as the AOT concentration increases, and a new band develops. This new band is attributed to the solute bound to the micelle interface. These changes allowed us to determine the binding constant (K_b) between these compounds and AOT. At W₀=[H₂O]/[AOT]=0 the values of K_b of 326±5 and 6.2±0.3 were found for the acid 2 and the alcohol 1, respectively. The strength of binding is interpreted considering their hydrogen-bond donor ability and the solubility in the organic pseudophase. For 1K_bdecreases as W₀ is increased, while for 2 no variation was observed. These effects are discussed in terms of carotenoid–water competition for interfacial binding sites.     

Interaction and photodynamic activity of cationic porphyrin derivatives bearing different patterns of charge distribution with GMP and DNA

The interaction of amphiphilic cationic porphyrins, containing different patterns of meso-substitution by 4-(3-N,N,N-trimethylammoniumpropoxy)phenyl (A) and 4-(trifluoromethyl)phenyl (B) groups, with guanosine 5′-monophosphate (GMP) and calf thymus DNA have been studied by optical methods in phosphate buffer solution. The properties of these synthetic porphyrins were compared with those of representative standard of anionic 5,10,15,20-tetra(4-sulphonatophenyl)porphyrin (TPPS₄⁴⁻) and cationic 5,10,15,20-tetra(4-N,N,N-trimethylammonium phenyl)porphyrin (TMAP⁴⁺). Stable complexes with GMP were found for cationic porphyrins, except for monocationic AB₃⁺. The binding constant (K_GMP  10⁴ M⁻¹) follows the order: A₃B³⁺  ABAB²⁺ > A₄⁴⁺  TMAP⁴⁺. Also, interaction with DNA was observed for all evaluated cationic porphyrins. For these related cationic porphyrins, the binding constant (K_DNA  10⁵ M⁻¹) increases with the number of cationic charges. On the other hand, the photodynamic activity of porphyrins was analyzed in solution of GMP and DNA. Monocationic AB₃⁺ is a less effective sensitizer to oxidize GMP in comparison with the other cationic porphyrins, in agreement with the lack of detected interaction with this nucleotide. The electrophoretic analysis of DNA indicates that photocleavage takes place when the samples are exposed to photoexcited tricationic and tetracationic porphyrins. In the presence of sodium azide the DNA decomposition was diminished. Also, reduction in the DNA photocleavage was observed under anoxic condition, indicating that oxygen is essential for DNA photocleavage sensitized by these cationic porphyrins. In addition, an increase in DNA degradation was not observed in deuteriated water. Therefore, an important contribution of type I photoreaction processes could be occurring in the DNA photodamage sensitized by these cationic porphyrins. These results provide a better understanding of the characteristics needed for sensitizers to produce efficient DNA photocleavage.     

1-Heptyne semihydrogenation catalysed by [PdCl2(NH2(CH2)5CH3)2]

The [PdCl₂(NH₂(CH₂)₅CH₃)₂] complex was tested as catalyst for 1-heptyne semihydrogenation under mild conditions of temperature and pressure in homogeneous and heterogeneous systems. Species were characterized by XPS and FTIR techniques. This revised version was published online in June 2006 with corrections to the Cover Date.     

Thermal analysis to assess pozzolanic activity of calcined kaolinitic clays

The use of calcined clays as partial replacement of cement is encouraged since it promotes the reduction of the green-house gas emission and the energy requirement of cement-based material, maintaining or enhancing the mechanical properties and the durable performance of these materials. In this paper, the use of thermal methods—DTA/TG and calorimetry—to select and to evaluate two kaolinitic clays for their use as pozzolanic materials was explored. The content and crystallinity of kaolinite in clays can be determined by DTA/TG analysis, and this technique is also suitable to select the calcination temperature for complete kaolinite dehydroxylation. Calorimetric analysis on blended cements (30 % by mass of replacement) can differentiate the reactivity of calcined kaolinitic clays. Results show that more reactive calcined kaolinitic clay develops the second and third peaks earlier than those of PC with great intensity and high acceleration. The reactivity of calcined clays is associated to raw materials containing kaolinite with high structural disorder that determines calcined clays with large specific surface area, high grindability, and small mean particles size (d ₅₀) for the same grinding objective. Finally, the DTA/TG analysis can determine the type and the amount of hydrated phases obtained at different ages to evaluate the pozzolanic reaction of calcined clay in accordance with the standardized pozzolanic activity index.     

Über Umlagerungen bei der Cyclialkylierung von Arylpentanolen zu 2,3‐Dihydro‐1H‐inden‐Derivaten, 5. Mitteilung

On Rearrangements by Cyclialkylations of Arylpentanols to 2,3‐Dihydro‐1 H ‐indene Derivatives. Part 5. The Acid‐Catalyzed Cyclialkylation of 2‐(2‐Chlorophenyl)‐2,4‐dimethylpentan‐3‐ol The mechanism proposed in [1] to explain the surprising result of the cyclialkylation of 4‐(2‐chlorophenyl)‐2,4‐dimethylpentan‐2‐ol ( 3 , R=Me), which gives not only the ‘normal' product, i.e., the 4‐chloro‐2,3‐dihydro‐1,1,3,3‐tetramethyl‐ ( 4 ), but also the isomer trans‐4‐chloro‐2,3‐dihydro‐1,1,2,3‐tetramethyl‐1H‐inden ( 5 ), could be differentiated in two sections (cf. Scheme 2): the first from 3 to the intermediary ion IIa ⇌ IIb , and the second from the latter ions to the final product 5 . For the first section, a sufficiently satisfactory explanation has been given in [1]; the second section has received important support from the mechanisms of the cyclialkylation of 2,4‐dimethyl‐2‐phenylpentan‐3‐ol ( 6 ), the precursor of II′a , the ion IIa without the o‐Cl substituent (cf. Schemes 2, 3 and 5 and [4]). The present communication gives an explanation of the influence of the o‐Cl substituent: a mechanism is proposed for the very complex cyclialkylation of 2‐(2‐chlorophenyl)‐2,4‐dimethylpentan‐3‐ol ( 11 ; cf. Scheme 9). Both mechanism may be considered as definitive. It is very surprising that, by the cyclialkylation of the compounds 1, 3, 8, 11, 15 , and 17 , only compound 1 gives the ‘normal' product; the cyclialkylation of all other phenylpentanols follows complex pathways including Et, i‐Pr, and Ph migrations, which could not be expected. In addition, it has been established that the transformation of 21 to 22 (cf. Scheme 12) and that of 23 to 24 (cf. Scheme 13) occur through two consecutive 1,2‐ and not through a single 1,3‐hydride migration or through an elimination‐addition process (cf. Scheme 13). It can be assumed that the transformation of ion IV (the 2‐(2‐chlorophenyl)‐3,4‐dimethylpent‐2‐ylium ion) to the ion V (the 4‐(2‐chlorophenyl)‐3,4‐dimethylpent‐2‐ylium ion (both shown in Scheme 9 as D‐isomers) occurs through the same pathway.