Geomorphology of a Portion of the Easternmost Ventura Basin

The Humphreys Quadrangle is a portion of the easternmost Ventura Basin underlain by a thick series of Tertiary sedimentary rocks. On these rocks a great variety of geomorphic forms have been molded by the processes of running water typical of a semi-arid climate and by several types of mass movement. Among the different categories of mass movement present, a new type, the siltflow, was observed.

The geomorphic forms of special interest present in the quadrangle are rock cones, open canyonheads, asymmetric canyons, and stream terraces and straths. The author urges the adoption of the definition of strath as that part of an old dissected valley floor, including the floors of tributary valleys, which was not part of the floodplain of the main valley stream.

An old erosion surface, the Puckett Mesa Surface, is present in the Humphreys Quadrangle which is correlative with certain of the older stream terraces. By correlating the variation of gradient and of fill of the stream terraces with post –Wisconsin climatic fluctuations the age of the Puckett Mesa Surface is set at approximately 6000 B.C. This correlation sets the probable age of the older Rancho La Brea deposits at 6000 to 8000 B. C. and the probable age of the Carpenteria brea deposits at 1000 to 1 B. C.

Late Transition Metals Supported by Aryl Ethers and Phenoxides Bearing Pendant Phosphines: Mechanistic Insights Relevant to Ether C-O Bond Cleavage

Terphenyl diphosphines bearing pendant ethers were prepared to provide mechanistic insight into the mechanism of activation of aryl C–O bonds with Group 9 and Group 10 transition metals. Chapters 2 and 3 of this dissertation describe the reactivity of compounds supported by the model phosphine and extension of this chemistry to heterogenous C–O bond activation.

Chapter 2 describes the synthesis and reactivity of aryl-methyl and aryl-aryl model systems. The metallation of these compounds with Ni, Pd, Pt, Co, Rh, and Ir is described. Intramolecular bond activation pathways are described. In the case of the aryl-methyl ether, aryl C–O bond activation was observed only for Ni, Rh, and Ir.

Chapter 3 outlines the reactivity of heterogenous Rh and Ir catalysts for aryl ether C–O bond cleavage. Using Rh/C and an organometallic Ir precursor, aryl ethers were treated with H2 and heat to afford products of hydrogenolysis and hydrogenation. Conditions were modified to optimize the yield of hydrogenolysis product. Hydrogenation could not be fully suppressed in these systems.

Appendix A describes initial investigations of bisphenoxyiminoquinoline dichromium compounds for selective C2H4 oligomerization to afford α-olefins. The synthesis of monometallic and bimetallic Cr complexes is described. These compounds are compared to literature examples and found to be less active and non-selective for production of α-olefins.

Appendix B describes the coordination chemistry of terphenyl diphosphines, terphenyl bisphosphinophenols, and biphenyl phosphinophenols proligands with molybdenum, cobalt, and nickel. Since their synthesis, terphenyl diphosphine molybdenum compounds have been reported to be good catalysts for the dehydrogenation of ammonia borane. Biphenyl phosphinophenols are demonstrated provide both phosphine and arene donors to transition metals while maintaining a sterically accessible coordination sphere. Such ligands may be promising in the context of the activation of other small molecules.

Appendix C contains relevant NMR spectra for the compounds presented in the preceding sections.