Effect of 2-Substitution on the Rearrangement of 1-Cyclopropylvinyl Cations

2-Substitution in 1-cyclopropylvinyl cations produces a steric effect on cation generation and solvent trapping, but an electronic charge-stabilizing effect on cyclopropyl-to-cyclobutyl rearrangement

Identification of Binuclear Acyl Complexes as Intermediates in the CO-induced Conversion of [(η^5-C_5H_5)Co(CO)(Me)]_2 into Acetone, and [(η^5-C_5H_5)Co(CO)(Et)]_2 into Pentan-3-one

Studies of the carbonylation of [(η^5-C_5H_5)Co(CO)(R)]_2(R = Me, Et) at temperatures below ambient have revealed that these complexes may be converted into ketones via binuclear diacyl complexes [(η^5-C_5H_5)Co(CO)(COR)]_2; the postulated mechanistic pathway circumvents the earlier-identified intermediate (η^5-C_5H_5)Co(CO)R_2, and involves alkyl transfer from a Co^(II) acyl complex as a critical step

Cationic Cyclization Involving a Remote Allene Function in the Trifluoroethanolysis of Hepta-5,6-dienyl Toluene-p-sulphonate

The remote allene function participates efficiently in the trifluoroethanolysis of hepta-5,6-dienyl toluene-p-sulphonate, leading to the cyclized 2-methylenecyclohexyl cation

Controlling dinitrogen functionalization at rhenium through alkali metal ion pairing

The rhenium(I) salt Na[Re(η⁵-Cp)(BDI)] can be cooled in solution under a dinitrogen atmosphere to selectively access complexes containing rhenium(III) centers bound to direduced, doubly-bonded N₂ (i.e. diazenide) fragments. We demonstrate this reactivity is critically dependent on ion pairing involving the Na⁺ ion in the starting material, as N₂ binding by Na[Re(η⁵-Cp)(BDI)] proved to be much less favorable when the Na⁺ was sequestered by benzo-12-crown-4. The analogous chemistry of Na[Re(η⁵-Cp)(BDI)] with carbon monoxide (CO) and 2,6-xylylisocyanide (XylNC) was also investigated, which provided structural and spectroscopic bases for determining the impact of ion pairing on π-acid activation in this system

On the Development of Catalytic Carba-6π Electrocyclizations

Hexatriene substrates substituted in the 2-position with carbonyl groups were studied in the context of catalytic 6π electrocyclizations. The nature of the carbonyl group and the substitution pattern on the hexatriene have significant effects on the ability of these substrates to succumb to catalysis. A novel 2-formyl hexatriene dimerization was observed. The first example of a catalytic asymmetric carba-6π electrocyclization is reported along with the discovery of an unusual kinetic resolution via a catalytic photochemical electrocyclic ring-opening

Electron acceptors promote proton–hydride tautomerism in low valent rhenium β-diketiminates

We report a series of β-diketiminate (BDI) complexes in which tautomeric rhenium(III) hydride and rhenium(I) protio-BDI species readily interconvert between the solid and solution states. This phenomenon, which is only operative when an electron-accepting ligand is bound to rhenium, was investigated by a combination of experimental and computational methods

The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations.

The effect of host structure on the selectivity and mechanism of intramolecular Prins reactions is evaluated using K12Ga4L6 tetrahedral catalysts. The host structure was varied by modifying the structure of the chelating moieties and the size of the aromatic spacers. While variation in chelator substituents was generally observed to affect changes in rate but not selectivity, changing the host spacer afforded differences in efficiency and product diastereoselectivity. An extremely high number of turnovers (up to 840) was observed. Maximum rate accelerations were measured to be on the order of 105, which numbers among the largest magnitudes of transition state stabilization measured with a synthetic host-catalyst. Host/guest size effects were observed to play an important role in host-mediated enantioselectivity

Obscuration in the Host Galaxies of Soft X-ray Selected Seyferts

We define a new sample of 96 low-redshift (z<0.1), soft X-ray selected Seyferts from the catalog of the Einstein Slew Survey (Elvis etal. 1992, Plummer et al. 1994). We probe the geometry and column depth of obscuring material in the host-galaxy disks using galaxian axial ratios determined mainly from the Digitized Sky Survey. The distribution of host-galaxy axial ratios clearly shows a bias against edge-on spirals, confirming the existence of a geometrically thick layer of obscuring material in the host-galaxy planes. Soft X-ray selection recovers some of the edge-on objects missed in UV and visible surveys but still results in 30% incompleteness for Type 1's. We speculate that thick rings of obscuring material like the ones we infer for these Seyferts might be commonly present in early type spirals, sitting at the Inner Lindblad Resonances of the nonaxisymmetric potentials of the host galaxies.Comment: 14 pages including 2 tables and 3 eps figures, aas2pp4.sty, to appear in Ap