Synthesis and characterisation of some new cyanonitrosyl chromium(l) complexes with phenetidines and anisidines

Summary A new series of cyano-substituted nitrosylchromium(I) complexes having octahedral stereochemistry around the metal ion, and of general formula, [CrNO(CN)₂(L)₂(H₂O)] (L =o-,m- andp-phenetidines oro-,m-, andp-anisidines) have been isolated in the solid state by interaction of potassium pentacy-anonitrosylchromate(I) monohydrate with the appropriately substituted aniline. The complexes, which have been characterised by elemental analysis, conductance, molecular weight determination, magnetic measurements, e.s.r. and i.r. spectral studies, contain chromium(I) in a low-spin d⁵-configuration.     

Solvation dynamics in Ni+ (H2O)n clusters probed with infrared spectroscopy

Infrared photodissociation spectroscopy is reported for mass-selected Ni+ (H2O)n complexes in the O-H stretching region up to cluster sizes of n = 25. These clusters fragment by the loss of one or more intact water molecules, and their excitation spectra show distinct bands in the region of the symmetric and asymmetric stretches of water. The first evidence for hydrogen bonding, indicated by a broad band strongly red-shifted from the free OH region, appears at the cluster size of n = 4. At larger cluster sizes, additional red-shifted structure evolves over a broader wavelength range in the hydrogen-bonding region. In the free OH region, the symmetric stretch gradually diminishes in intensity, while the asymmetric stretch develops into a closely spaced doublet near 3700 cm(-1). The data indicate that essentially all of the water molecules are in a hydrogen-bonded network by the size of n = 10. However, there is no evidence for the formation of clathrate structures seen recently via IR spectroscopy of protonated water clusters.     

Regioselective synthesis of indenols via nickel-catalyzed carbocyclization reaction

2-Halophenyl ketones 1a-e (1a, o-IC(6)H(4)COCH(3)) undergo carbocyclization with alkyl propiolates (2a, CH(3)(CH(2))(4)C[triple bond]CCO(2)CH(3); 2b, TMSC[triple bond]CCO(2)Et 2c, CH(3)C[triple bond]CCO(2)CH(3); 2d, CH(3)OCH(2)C[triple bond]CCO(2)CH(3); 2e, CH(3)(CH(2))(3)C[triple bond]CCO(2)CH(3); 2f, PhC[triple bond]CCO(2)CH(3); and 2g, (CH(3))(3)C[triple bond]CCO(2)CH(3)) in the presence of Ni(dppe)Br(2) and zinc powder in acetonitrile at 80 degrees C to afford the corresponding indenol derivatives 3a-m with remarkable regioselectivity in good to excellent yields. The nickel-catalyzed carbocyclization reaction was successfully extended to other simple disubstituted alkynes. Thus, the reaction of 2-halophenyl ketones 1a-e with disubstituted alkynes (2h, PhC[triple bond]CPh; 2i, CH(3)C(6)H(4)C[triple bond]CC(6)H(4)CH(3); 2j, CH(3)CH(2)C[triple bond]CCH(2)CH(3); 2k, PhC[triple bond]CCH(3); 2l, TMSC[triple bond]CCH(3); and 2m, PhC[triple bond]C(CH(2))(3)CH(3)) proceeded smoothly to afford the corresponding indenols 4a-t in good to excellent yields. For unsymmetrical alkynes 2k-m, the carbocyclization gave two regioisomers with regioselectivities ranging from 1:2 to 1:12 depending on the substituents on the alkyne and on the aromatic ring of halophenyl ketone. A possible mechanism for this nickel-catalyzed carbocyclization reaction is also proposed.     

Kinetics and mechanism of the oxidation of 2-furancarbox-aldehyde by thallium(III) in perchloric acid solutions

The kinetics of the oxidation of 2-furancarboxaldehyde by thallic perchlorate at 50°C obeys the rate law

Distorted Phthalocyanines by Click Chemistry: Photoacoustic,Photothermal, and Surface-Enhanced Resonance Raman Studies

Distortion of nominally planar phthalocyanine macrocycles affects the excited state dynamics in that most of the excited-state energy decays through internal conversion. A click-type annulation reaction on a perfluorophthalocyanine platform appending a seven-membered ring to the β-positions on one or more of the isoindoles distorts the macrocycle and modulates solubility. The distorted derivative enables photoacoustic imaging, photothermal effects, and strong surface-enhanced resonance Raman signals.     

Graphene oxide‐catalyzed CSp3–H activation of methylarenes in aqueous medium: A unified metal‐free access to amides and benzimidazoles

Graphene oxide (GO)‐catalyzed selective synthesis of amides via C_Sp3–H activation of methylarenes and consequent C–N bond formation with anilines under aqueous medium has been described. Oxygen functionality allied with GO surface played a dual role both as acid catalyst and oxidizing agent to some extent. However, GO has a copious effect on the reaction, shown by a high TOF value with TBHP as co‐oxidant. The decisive role of carboxylic acid functional groups on GO nanosheets in this metal‐free strategy has been confirmed and was monitored by various analytic techniques viz. Fourier transform‐infrared, UV–Vis, Raman and XPS. A plausible mechanism was proposed by control experiments and by the isolation of the intermediate. Over‐oxidation of methylarenes was not detected, and high recyclability of the carbocatalyst with its heterogeneous behavior facilitated the isolation and purification of the desired products. We have further explored the utility of this process for the chemoselective synthesis of benzimidazoles.     

Regioselective Photocyclization Reactions of 3‐Allyloxy‐6‐chloro‐2‐(thiophen‐3‐yl)‐4H‐chromen‐4‐one: Solvent Effect

The photo‐irradiation of thienylchromenone resulted in the regioselective cyclization which is exclusively controlled by the nature of solvent used as reaction medium. Compared to nonpolar medium, polar solvent furnished a diverse array of novel angular tetracyclic photoproducts with gem‐dihydro functionality and exocyclic double bonds on the fused pyran ring, which is unprecedented to best of our knowledge.     

Synthesis of N-Acyl Triazolyl-Pyrazolines via Acylation Initiated by the Hydrazone Moiety with Carboxylic Acids

An efficient synthesis of N-acyl/N-substituted acyl pyrazolines and their triazole hybrids have been accomplished via acylation of pyrazolines and pyrazoline-triazole hybrids with carboxylic acids and/or substituted carboxylic acids in the absence of activating agents/catalysts. In the present study, a mechanism envisaging the in situ generation of a new transient acylating intermediate has been proposed to explain the acylation.     

The possibility of semiconductor–metal transition in a spherical quantum dot

We observe an abrupt change in diamagnetic susceptibility at critical donor concentration for an $\text{ Al }_\mathrm{x}\text{ Ga }_\mathrm{1-x}\text{ As/GaAs }$ Al x Ga 1 ? x As/GaAs quantum dot system in the effective mass approximation indicating a possible semiconductor metal transition. The effect of confining potential and the laser intensity on the abrupt change in diamagnetic susceptibility has also been studied. The effect of nonparabolicity of the conduction band has been included in our calculations. Results are presented and discussed.