Mixed-metal cluster chemistry. 19. Crystallographic, spectroscopic, electrochemical, spectroelectrochemical, and theoretical studies of systematically varied tetrahedral group 6-iridium clusters

A systematically varied series of tetrahedral clusters involving ligand and core metal variation has been examined using crystallography, Raman spectroscopy, cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry, and approximate density functional theory, to assess cluster rearrangement to accommodate steric crowding, the utility of metal-metal stretching vibrations in mixed-metal cluster characterization, and the possibility of tuning cluster electronic structure by systematic modification of composition, and to identify cluster species resultant upon electrochemical oxidation or reduction. The 60-electron tetrahedral clusters MIr(3)(CO)(11-x)(PMe(3))(x)(eta(5)-Cp) [M = Mo, x = 0, Cp = C(5)H(4)Me (5), C(5)HMe(4) (6), C(5)Me(5) (7); M = W, Cp = C(5)H(4)Me, x = 1 (13), x = 2 (14)] and M(2)Ir(2)(CO)(10-x)(PMe(3))(x)(eta(5)-Cp) [M = Mo, x = 0, Cp = C(5)H(4)Me (8), C(5)HMe(4) (9), C(5)Me(5) (10); M = W, Cp = C(5)H(4)Me, x = 1 (15), x = 2 (16)] have been prepared. Structural studies of 7, 10, and 13 have been undertaken; these clusters are among the most sterically encumbered, compensating by core bond lengthening and unsymmetrical carbonyl dispositions (semi-bridging, semi-face-capping). Raman spectra for 5, 8, WIr(3)(CO)(11)(eta(5)-C(5)H(4)Me) (11), and W(2)Ir(2)(CO)(10)(eta(5)-C(5)H(4)Me)(2) (12), together with the spectrum of Ir(4)(CO)(12), have been obtained, the first Raman spectra for mixed-metal clusters. Minimal mode-mixing permits correlation between A(1) frequencies and cluster core bond strength, frequencies for the A(1) breathing mode decreasing on progressive group 6 metal incorporation, and consistent with the trend in metal-metal distances [Ir-Ir < M-Ir < M-M]. Cyclic voltammetric scans for 5-15, MoIr(3)(CO)(11)(eta(5)-C(5)H(5)) (1), and Mo(2)Ir(2)(CO)(10)(eta(5)-C(5)H(5))(2) (3) have been collected. The [MIr(3)] clusters show irreversible one-electron reduction at potentials which become negative on cyclopentadienyl alkyl introduction, replacement of molybdenum by tungsten, and replacement of carbonyl by phosphine. These clusters show two irreversible one-electron oxidation processes, the easier of which tracks with the above structural modifications; a third irreversible oxidation process is accessible for the bis-phosphine cluster 14. The [M(2)Ir(2)] clusters show irreversible two-electron reduction processes; the tungsten-containing clusters and phosphine-containing clusters are again more difficult to reduce than their molybdenum-containing or carbonyl-containing analogues. These clusters show two one-electron oxidation processes, the easier of which is reversible/quasi-reversible, and the more difficult of which is irreversible; the former occur at potentials which increase on cyclopentadienyl alkyl removal, replacement of tungsten by molybdenum, and replacement of phosphine by carbonyl. The reversible one-electron oxidation of 12 has been probed by UV-vis-NIR and IR spectroelectrochemistry. The former reveals that 12(+) has a low-energy band at 8000 cm(-1), a spectrally transparent region for 12, and the latter reveals that 12(+) exists in solution with an all-terminal carbonyl geometry, in contrast to 12 for which an isomer with bridging carbonyls is apparent in solution. Approximate density functional calculations (including ZORA scalar relativistic corrections) have been undertaken on the various charge states of W(2)Ir(2)(CO)(10)(eta(5)-C(5)H(5))(2) (4). The calculations suggest that two-electron reduction is accompanied by W-W cleavage, whereas one-electron oxidation proceeds with retention of the tetrahedral core geometry. The calculations also suggest that the low-energy NIR band of 12(+) arises from a sigma(W-W) --> sigma*(W-W) transition.     

The fluoro analogue of Wilkinson's catalyst and unexpected Ph-Cl activation

The fluoro analogue of Wilkinson's catalyst, [(Ph3P)3RhF] (1), was synthesized and fully characterized. Both solution behavior and solid-state geometry parameters of 1 were found to be surprisingly similar to those of Wilkinson's catalyst. Unlike Wilkinson's catalyst however, 1 exhibited most unusual reactivity toward the notoriously inert C-Cl bond of nonactivated chloroarenes. The novel Ph-Cl activation with 1 includes fluorine transfer from the metal to a phosphine ligand and evidently phenyl transfer from the phosphine to Rh to produce an electron-rich sigma-phenylrhodium intermediate.     

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn-Teller effect

Single-crystal Raman spectra are presented for the salt [C(NH2)3][V(OH2)6](SO4)2, displaying electronic transitions between the trigonal components of the vanadium(III) 3T1g(Oh) ground term. The 3A-->3E(C3) electronic Raman band is centered at approximately 2720 cm-1, and exhibits extensive structure, revealing the energies of the spinor components of the 3E(C3) term for the two crystallographically distinct [V(OH2)6]3+ cations. The data are interpreted in conjunction with parameters previously reported from an electron paramagnetic resonance study of the salt. A satisfactory reproduction of the electronic Raman profile and ground-state spin-Hamiltonian parameters is achieved by employing a (3A plus sign in circle3E)multiply sign in circle e vibronic coupling model, in which the spin-orbit splitting of the 3E(C3) is quenched significantly by the Ham effect, and the intensity of harmonics of the Jahn-Teller active vibration enhanced by their proximity to the electronic Raman bands. The model gives an excellent account of the intensities of the electronic Raman bands, which are shown to depend profoundly on both temperature and the selected component of the polarizability tensor. The electronic Raman profile changes notably upon deuteriation, a result that exposes deficiencies in the single-mode coupling model.     

INVESTIGATION OF THE ANTIVIRAL ACTION OF THE PHOTOACTIVE COMPOUND PHENYLHEPTATRIYNE

Abstract— Murine cytomegalovirus, a herpes virus, was used as a model virus to investigate the mechanism of the anti-viral action of phenylheptatriyne in long wave ultraviolet light. The genome and proteins of the inactivated virus penetrated the nuclei of susceptible cells normally. Furthermore, the viral genome did not contain extra single strand breaks or cross-links. However, cells infected with the treated virus did not synthesize late viral proteins, as determined by polyacrylamide gel electrophoresis. nor did they synthesize late viral RNA and viral DNA according to nucleic acid hybridization tests. Thus the compound may interfere with an early viral function so that the replication cycle cannot proceed.     

Trace level analysis of volatile and semi-volatile organic compounds in water using a membrane/jet separator interfaced to an ion trap mass spectrometer

An ion trap mass spectrometer, equipped with a membrane/jet separator interface, is used for the direct detection of volatile and semi-volatile organic compounds in aqueous solutions. Aqueous sample is passed through a capillary membrane, the outside surface of which is continuously purged by helium. The permeate is pneumatically transported to the mass spectrometer via a jet separator which acts as an additional enrichment device. The performance and response characteristics of non-porous silicone and microporous polytetrafluoroethylene (PTFE) membranes are studied. The microporous membrane allows sufficient water to pass for it to be used as a reagent gas for chemical ionization. Both types of membranes provide detection limits in the parts per trillion (pptr) to parts per billion (ppb) range with a linear dynamic range of 3 orders of magnitude for some volatile organic compounds. Results show that there is no detectable matrix effect on response in the selected cases examined. The use of microporous membranes to analyze more polar compounds, such as 5-hydroxymethyl furfuraldehyde and lactic acid, is also demonstrated. The effects of other experimental parameters, such as membrane temperature and length, on sensitivity are also investigated.     

STRUCTURE-ACTIVITY STUDIES OF PHOTOACTIVATED ANTIVIRAL AND CYTOTOXIC TRICYCLIC THIOPHENES

The photoactivated antiviral and cytotoxic activities of the naturally occurring thiophene, alpha-terthienyl (1), and 15 synthetic analogues were evaluated against murine cytomegalovirus and Sindbis virus, and murine mastocytoma cells. After irradiation with near UV light, alpha-terthienyl and most of its analogues had significant toxicity, with minimum inhibitory concentrations in the range of 0.02-40 microM. In the absence of near UV irradiation, only one analogue had antiviral activity and five were cytotoxic. The most active analogues were those containing carboxylic acid, hydroxyl, or cyano substituents. Quantitative structure-activity relationship analysis of thiophene phototoxicity suggested that the rate of singlet oxygen production is the primary determinant of antiviral and cytotoxic activities. For phototoxicity against murine cytomegalovirus, a significant role for hydrophobicity was also demonstrated. Tricyclic thiophenes show significant potential for photochemotherapy of viral infections and cancer, and further evaluation in animal models is recommended.     

Effects of Added Surfactant on the Dynamic Interfacial Tension Behavior of Acidic Oil/Alkaline Systems

The effects of a ready-made surfactant (sodium dodecyl sulfate) on the dynamic interfacial tension between a model acidic oil (linoleic acid dissolved in paraffin oil) and various aqueous alkaline (NaOH) systems have been studied using pendant drop tensiometry at surfactant concentrations both below and above the critical micelle concentration (CMC). Below the CMC the added surfactant contributes significantly to a further reduction of interfacial tension of the reacting acid/alkaline system, whereas above the CMC the added surfactant plays an important role in damping the dynamic trends observed for the reactive system alone. Copyright 2001 Academic Press.     

Post-lactonization of vinyl polymers containing pendent ester and hydroxymethyl groups

Copolymers of methyl methacrylate with methyl and ethyl α-hydroxymethylacrylate and with α-hydroxymethylstyrene have been prepared with free-radical initiators at temperatures below 80°C. At higher reaction temperatures or under extrusion conditions, alcohol was eliminated and the free hydroxyl content was greatly decreased. All evidence indicates the formation of six-membered lactone groups in this post-polymerization reaction: direct evidence for their formation is lacking, however, since neither infrared nor nuclear magnetic resonance spectra could be used to detect lactonization in this system. The loss of activity from ¹⁴C ester-labeled methyl methacrylate copolymer on heating could be correlated with the extent of lactonization. The degree of lactonization is relatively less with copolymers containing higher amounts of hydroxymethyl groups. The resulting polymers exhibit higher heat distortion temperatures and decreased impact resistance when compared to poly(methyl methacrylate). Attempts were made to incorporate similar lactone structures by cyclocopolymerization with methyl methacrylate of α-methacryloxymethylstyrene or ethyl α-methacryloxymethylacrylate, but only crosslinked polymers or polymers with pendent unsaturation were found.