Reactivity of γ-chloro-gem-trichloroalkanes with chromous chloride

CrCl₂-mediated condensation of γ-chloro-gem-trichloroalkanes with aldehyde generates homoallylic alcohols through a hydride rearrangement followed by a Nozaki-Hiyama allylation.     

Unstable minimal surfaces and Heegaard splittings

Partially supported by NSF grant DMS-8701746     

Pythagorean euclidean four point properties

Characterizations of real inner product spaces among a class of metric spaces have been obtained based on homogeneity of metric pythagorean orthogonality, a metrization of the concept of pythagorean orthogonality as defined in normed linear spaces. In the present paper a considerable weakening of this hypothesis is shown to characterize real inner product spaces among complete, convex, externally convex metric spaces, generalizing a result of Kapoor and Prasad [9], and providing a connection with the many characterizations of such spaces using euclidean four point properties.     

Characterization of supercommuting matrices

For a given n-by-n matrix A, we consider the set of matrices which commute with A and all of whose principal submatrices commute with the corresponding principal submatrices of A. The properties of this set are examined, with particular attention to its dimension.     

Space tilings and local isomorphism

We prove for a large class of tilings that, given a finite tile set, if it is possible to tile Euclideann-space with isometric copies of this set, then there is a tiling with the ‘local isomorphism property’. Research supported in part by NSF Grant No. DMS-9001475.     

The thermolysis of dicarbonylcyclopentadienyliron dimer: The formation of biferrocene

The thermolysis of dicarbonylcyclopentadienyliron dimer in a sealed tube at 300°C has been reported to produce ferrocene, carbon monoxide, carbon dioxide, cyclopentadiene and elemental iron. We observe in addition to these products the production of biferrocene and elemental carbon. Thermolysis of carbonylcyclopentadienyliron tetramer (produced from the dimer by thermolysis in refluxing xylene) produces ferrocene, iron and carbon monoxidre; no biferrocene, carbon dioxide or elemental carbon are produced. A scheme is proposed to account for these products.     

A convenient method for regioselective C-5 halogenation of 4(3H)-oxo-7H-pyrrolo[2,3-d]pyrimidines

N-7, O-Disilylation of 4(3H)-oxo-7H-pyrrolo[2,3-d]pyrimidines provides a convenient method for activation of these compounds toward regiospecific halogenation at C-5. The sequence is conveniently carried out without isolation of the silylated derivatives and desilylation is spontaneous upon addition of water to the reaction mixture.     

The use of sulfide cluster-derived catalysts to understand the promotional effect in hydrotreatment catalysis

Sulfide cluster-derived ensembles are promising models of the active sites in commercial hydrotreatment catalysts. A series of sulfide clusters were adsorbed intact onto high-surface-area γ-alumina, magnesium oxide and activated carbon supports, then pretreated to produce highly dispersed catalytic ensembles with sizes similar to those of their precursor clusters. The activities of the bimetallic cluster-derived catalysts were significantly higher than those of the monometallic catalysts. We took this as evidence that direct interactions between molybdenum and the promoter element cause the promotional effect observed in commercial hydrotreatment catalysts. The hydrodesulfurization and hydrodenitrogenation activities correlated with the extent of molybdenum reduction. Our results suggested that the active sites in promoted hydrotreatment catalysts are centered on molecular-scale ensembles containing molybdenum, sulfur and the promoter element.     

Surface enhanced Raman scattering from mildly roughened surfaces: variation of signal with metal grain size

The intensity of surface enhanced Raman scattering from benzoic acid derivatives on mildly roughened, thermally evaporated Ag films shows a remarkably strong dependence on metal grain size. Large grained (slowly deposited) films give a superior response, by up to a factor of 10, to small grained (quickly deposited) films, with films of intermediate grain size yielding intermediate results. The optical field amplification underlying the enhancement mechanism is due to the excitation of surface plasmon polaritons (SPPs). Since surface roughness characteristics, as determined by STM, remain relatively constant as a function of deposition rate, it is argued that the contrast in Raman scattering is due to differences in elastic grain boundary scattering of SPPs (leading to different degrees of internal SPP damping), rather than differences in the interaction of SPPs with surface inhomogeneities.