ESR. Spectra and Structures of Radical Anions in the Dibenzo[a,e]cyclooctene Series

ESR. studies are reported for the radical anions of 5,6-didehydro- and 5,6,11,12-tetradehydro-dibenzo[a,e]cyclooctene (III and IV, resp.), in addition to that of dibenzo[a,e]cyclooctene (II) itself, the spectrum of which has been reexamined. Comparison of the proton and ¹³C coupling constants for II·?, III·? and IV·? indicates that the three radical anions do not differ greatly in their electronic and molecular structures. This statement implies that II·? should also be substantially planar, i.e., the tub-shaped eight-membered ring in II is expected to flatten on passing from the neutral molecule to its radical anion. Support for postulating such a change in geometry, analogous to that encountered with the parent cyclooctatetraene (I), is provided by INDO calculations.     

Intramolecular interaction effects and the structure of N2OS and N2O2: An Ab initio study

An ab initio study of O?N? N?S with full geometry optimization has been carried out to corroborate the presence of an interaction between the terminal atoms in this type of structure, which, in O?N? N?O, apparently stabilizes the cis conformer. Using the unscaled 4–31G basis set with a full set of d functions on the sulfur, there is a potential minimun at the trans but not the cis geometry. A gauche conformer with a torsional angle of 77.2° is the most stable. With N₂O₂ this basis set gives potential minima at both the cis and trans geometries, but the trans conformer is slightly more stable, contrary to experiment and the results of (7,3) basis-set calculations reported in the literature in which Gaussian lobe functions were employed. Using a (9,5) basis set there is no longer a potential minimum at the cis geometry, and a gauche structure is more stable than the cis conformer as in the case of N₂OS with the less-extended basis set. Force constants (harmonic and anharmonic), compliance constants, relaxed force constants, and interaction-displacement coordinates for both molecules are compared for key structural elements.     

Syntheses and conformational analyses of some 3-amino-2,5-dioxo-2,3,4,5-tetrahydro-1H-1-benzazepine derivatives: X-ray crystal structure of 35–3-[[(1,1-dimethylethoxy)carbonyl]amino]-2,5-dioxo-2,3,4,5-tetrahydro-1H-1-benzazepine

The constrained dipeptide mimic 1 was synthesized from 2 in three steps with 65% overall yield. Analyses of the ¹H nmr data of a number of 3-amino-2,5-dioxo-2,3,4,5-tetrahydro-1H-1-benzazepine derivatives led to the conclusion that these compounds adopt a similar conformation and that this ring system is rigid. X-ray crystallography was used to define the structure of 3 , and computer-aided energy minimization of 6 gave a preferred conformation similar to that observed in the crystal of 3 .     

In vivo microdialysis/liquid chromatography/tandem mass spectrometry for the on-line monitoring of melatonin in rat

Liquid chromatography/tandem mass spectrometry (LC/MS/MS) has been coupled to in vivo microdialysis for on-line monitoring of melatonin in a freely moving rat for a period of 15 hours. A microdialysis probe was surgically implanted into the jugular vein of the rat, and deionized water was used as the perfusion medium at a flow rate of 1.0 microL/min. Microdialysis samples were collected in an on-line injector with sample injection every 30 minutes. Melatonin was dosed by intraperitoneal (i.p.) injection and then monitored by microdialysis/LC/MS/MS. The whole experiment, including the microdialysis sampling and sample injection into the LC/MS system, was fully automated. Metabolites of melatonin were identified off-line by LC/MSn experiments. Two metabolites were identified as 6-hydroxymelatonin and cyclic 2-hydroxymelatonin, consistent with ones found previously in the literature.     

Nuclear magnetic resonance study of the molecular structure of 1,3-benzodioxole and 1,3-indandione partially oriented in nematic solvents

The molecular structures of 1,3-benzodioxole and 1,3-indandione partially oriented in nematic solvents have been studied by NMR. Results for 1,3-indandione agree well with a planar model. The structural parameters are similar to those obtained by X-ray studies. No keto-enol tautomerism is observed. An anomalous structural result is obtained for 1,3-benzodioxole if the molecule is assumed to be planar. Dipolar couplings agree well with puckered model. The puckering angle is found to be about 15.5° ± 2°, similar to the values observed for TTF, TSeF and 2,5-dihydrofuran.     

A NMR study of tetrathiofulvalene and tetracyanoquinodimethane: relative proton geometries and order parameters using nematic solvents; carbon-proton spin spin coupling constants for TTF

From proton magnetic resonance spectra of TTF and TCNQ partially oriented in nematic liquid crystal solvents the ratio of length to width of the proton rectangle is 3.124 ± 0.03 for TTF and 1.765 ± 0.024 for TCNQ. Values of J_CH obtained for TTF dissolved in d₆-acetone, are J_CH = 187.9 ± 0.3 Hz, J_CCH = 6.7 ±0.1 Hz and J_CSCH = 9.0 ±0.2 Hz.     

The synthesis and reactivity of the heptanuclear dianion [Os7(CO)20]2− including the synthesis and structural characterizations of the compounds [Os7(CO)20(AuPEt)3 2] and [Os8(CO)20(η6-C6H6]

Reduction of the heptaosmium cluster [Os₇(CO)₂₁] With [Et₄N][NH₄) gives the cluster dianion [Os₇(CO)₂₀]^2–,1, in high yield. The reaction of the dianion with [AuPR ₃Cl] (R=Et or Ph) in the presence of TlPF₆ forms [Os₇((CO)₂₀(AuPR ₃)₂] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C₆H₆)(CH₃CN)₃]²⁺ gives [Os₈(CO)₂₀ ( ⁶-C₆H₆)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph₄P]⁺ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt₃ groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C₆H₆) unit capped to a triangular face, to give a bicapped octahedral framework.