Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.

Indentification and characterization of a novel CA^(2+)-binding protein in avian erythrocytes

A novel Ca^(2+)-binding protein with Mr of 23 K (designated p23) has been identified in avian erythrocytes and thrombocytes. p23 localizes to the marginal bands (MBs), centrosomes and discrete sites around the nuclear membrane in mature avian erythrocytes. p23 appears to bind Ca^(2+) directly and its interaction with subcellular organelles seems to be modulated by intracellular [Ca^(2+)]. However, its unique protein sequence lacks any known Ca^(2+)-binding motif. Developmental analysis reveals that p23 association to its target structures occurs only at very late stages of bone marrow definitive erythropoeisis. In primitive erythroid cells, p23 distributes diffusely in the cytoplasm and lacks any distinct localization. It is postulated that p23 association to subcellular structures may be induced in part by decreased intracellular [Ca^(2+)]. In vitro and in vivo experiments indicate that p23 does not appear to act as a classical microtubule-associated protein (MAP) but p23 homologues appear to be expressed in MB-containing cells of a variety of species from different vertebrate classes. It has been hypothesized that p23 may play a regulatory role in MB stabilization in a Ca^(2+)-dependent manner.

Binucleated (bnbn) turkey erythrocytes were found to express a truncated p23 variant (designated p21) with identical subcellular localization as p23 except immunostaining reveals the presence of multi-centrosomes in bnbn cells. The p21 sequence has a 62 amino acid deletion at the C-terminus and must therefore have an additional ~40 amino acids at the N-terminus. In addition, p21 seems to have lost the ability to bind Ca^(2+) and its supramolecular interactions are not modulated by intracellular [Ca^(2+)]. These apparent differences between p23 and p21 raised the possibility that the p23/p21 allelism could be the Bn/bn genotype. However, genetic analysis suggested that p23/p21 allelism had no absolute correlation with the Bn/bn genotype.

Dating and characterizing late holocene earthquakes using paleomagnetics

In this thesis I apply paleomagnetic techniques to paleoseismological problems. I investigate the use of secular-variation magnetostratigraphy to date prehistoric earthquakes; I identify liquefaction remanent magnetization (LRM), and I quantify coseismic deformation within a fault zone by measuring the rotation of paleomagnetic vectors.

In Chapter 2 I construct a secular-variation reference curve for southern California. For this curve I measure three new well-constrained paleomagnetic directions: two from the Pallett Creek paleoseismological site at A.D. 1397-1480 and A.D. 1465-1495, and one from Panum Crater at A.D. 1325-1365. To these three directions I add the best nine data points from the Sternberg secular-variation curve, five data points from Champion, and one point from the A.D. 1480 eruption of Mt. St. Helens. I derive the error due to the non-dipole field that is added to these data by the geographical correction to southern California. Combining these yields a secular variation curve for southern California covering the period A.D. 670 to 1910, with the best coverage in the range A.D. 1064 to 1505.

In Chapter 3 I apply this curve to a problem in southern California. Two paleoseismological sites in the Salton trough of southern California have sediments deposited by prehistoric Lake Cahuilla. At the Salt Creek site I sampled sediments from three different lakes, and at the Indio site I sampled sediments from four different lakes. Based upon the coinciding paleomagnetic directions I correlate the oldest lake sampled at Salt Creek with the oldest lake sampled at Indio. Furthermore, the penultimate lake at Indio does not appear to be present at Salt Creek. Using the secular variation curve I can assign the lakes at Salt Creek to broad age ranges of A.D. 800 to 1100, A.D. 1100 to 1300, and A.D. 1300 to 1500. This example demonstrates the large uncertainties in the secular variation curve and the need to construct curves from a limited geographical area.

Chapter 4 demonstrates that seismically induced liquefaction can cause resetting of detrital remanent magnetization and acquisition of a liquefaction remanent magnetization (LRM). I sampled three different liquefaction features, a sandbody formed in the Elsinore fault zone, diapirs from sediments of Mono Lake, and a sandblow in these same sediments. In every case the liquefaction features showed stable magnetization despite substantial physical disruption. In addition, in the case of the sandblow and the sandbody, the intensity of the natural remanent magnetization increased by up to an order of magnitude.

In Chapter 5 I apply paleomagnetics to measuring the tectonic rotations in a 52 meter long transect across the San Andreas fault zone at the Pallett Creek paleoseismological site. This site has presented a significant problem because the brittle long-term average slip-rate across the fault is significantly less than the slip-rate from other nearby sites. I find sections adjacent to the fault with tectonic rotations of up to 30°. If interpreted as block rotations, the non-brittle offset was 14.0+2.8, -2.1 meters in the last three earthquakes and 8.5+1.0, -0.9 meters in the last two. Combined with the brittle offset in these events, the last three events all had about 6 meters of total fault offset, even though the intervals between them were markedly different.

In Appendix 1 I present a detailed description of my standard sampling and demagnetization procedure.

In Appendix 2 I present a detailed discussion of the study at Panum Crater that yielded the well-constrained paleomagnetic direction for use in developing secular variation curve in Chapter 2. In addition, from sampling two distinctly different clast types in a block-and-ash flow deposit from Panum Crater, I find that this flow had a complex emplacement and cooling history. Angular, glassy "lithic" blocks were emplaced at temperatures above 600° C. Some of these had cooled nearly completely, whereas others had cooled only to 450° C, when settling in the flow rotated the blocks slightly. The partially cooled blocks then finished cooling without further settling. Highly vesicular, breadcrusted pumiceous clasts had not yet cooled to 600° C at the time of these rotations, because they show a stable, well clustered, unidirectional magnetic vector.

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.