Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

Studies in nuclear reactor dynamics : I. The accuracy of point kinetics. II. The effect of delayed neutrons on the spectrum of the group-diffusion operator

This thesis is a theoretical work on the space-time dynamic behavior of a nuclear reactor without feedback. Diffusion theory with G-energy groups is used.

In the first part the accuracy of the point kinetics (lumped-parameter description) model is examined. The fundamental approximation of this model is the splitting of the neutron density into a product of a known function of space and an unknown function of time; then the properties of the system can be averaged in space through the use of appropriate weighting functions; as a result a set of ordinary differential equations is obtained for the description of time behavior. It is clear that changes of the shape of the neutron-density distribution due to space-dependent perturbations are neglected. This results to an error in the eigenvalues and it is to this error that bounds are derived. This is done by using the method of weighted residuals to reduce the original eigenvalue problem to that of a real asymmetric matrix. Then Gershgorin-type theorems .are used to find discs in the complex plane in which the eigenvalues are contained. The radii of the discs depend on the perturbation in a simple manner.

In the second part the effect of delayed neutrons on the eigenvalues of the group-diffusion operator is examined. The delayed neutrons cause a shifting of the prompt-neutron eigenvalue s and the appearance of the delayed eigenvalues. Using a simple perturbation method this shifting is calculated and the delayed eigenvalues are predicted with good accuracy.

Determination of source finiteness and depth of large earthquakes

In this thesis, a method to retrieve the source finiteness, depth of faulting, and the mechanisms of large earthquakes from long-period surface waves is developed and applied to several recent large events.

In Chapter 1, source finiteness parameters of eleven large earthquakes were determined from long-period Rayleigh waves recorded at IDA and GDSN stations. The basic data set is the seismic spectra of periods from 150 to 300 sec. Two simple models of source finiteness are studied. The first model is a point source with finite duration. In the determination of the duration or source-process times, we used Furumoto's phase method and a linear inversion method, in which we simultaneously inverted the spectra and determined the source-process time that minimizes the error in the inversion. These two methods yielded consistent results. The second model is the finite fault model. Source finiteness of large shallow earthquakes with rupture on a fault plane with a large aspect ratio was modeled with the source-finiteness function introduced by Ben-Menahem. The spectra were inverted to find the extent and direction of the rupture of the earthquake that minimize the error in the inversion. This method is applied to the 1977 Sumbawa, Indonesia, 1979 Colombia-Ecuador, 1983 Akita-Oki, Japan, 1985 Valparaiso, Chile, and 1985 Michoacan, Mexico earthquakes. The method yielded results consistent with the rupture extent inferred from the aftershock area of these earthquakes.

In Chapter 2, the depths and source mechanisms of nine large shallow earthquakes were determined. We inverted the data set of complex source spectra for a moment tensor (linear) or a double couple (nonlinear). By solving a least-squares problem, we obtained the centroid depth or the extent of the distributed source for each earthquake. The depths and source mechanisms of large shallow earthquakes determined from long-period Rayleigh waves depend on the models of source finiteness, wave propagation, and the excitation. We tested various models of the source finiteness, Q, the group velocity, and the excitation in the determination of earthquake depths.

The depth estimates obtained using the Q model of Dziewonski and Steim (1982) and the excitation functions computed for the average ocean model of Regan and Anderson (1984) are considered most reasonable. Dziewonski and Steim's Q model represents a good global average of Q determined over a period range of the Rayleigh waves used in this study. Since most of the earthquakes studied here occurred in subduction zones Regan and Anderson's average ocean model is considered most appropriate.

Our depth estimates are in general consistent with the Harvard CMT solutions. The centroid depths and their 90 % confidence intervals (numbers in the parentheses) determined by the Student's t test are: Colombia-Ecuador earthquake (12 December 1979), d = 11 km, (9, 24) km; Santa Cruz Is. earthquake (17 July 1980), d = 36 km, (18, 46) km; Samoa earthquake (1 September 1981), d = 15 km, (9, 26) km; Playa Azul, Mexico earthquake (25 October 1981), d = 41 km, (28, 49) km; El Salvador earthquake (19 June 1982), d = 49 km, (41, 55) km; New Ireland earthquake (18 March 1983), d = 75 km, (72, 79) km; Chagos Bank earthquake (30 November 1983), d = 31 km, (16, 41) km; Valparaiso, Chile earthquake (3 March 1985), d = 44 km, (15, 54) km; Michoacan, Mexico earthquake (19 September 1985), d = 24 km, (12, 34) km.

In Chapter 3, the vertical extent of faulting of the 1983 Akita-Oki, and 1977 Sumbawa, Indonesia earthquakes are determined from fundamental and overtone Rayleigh waves. Using fundamental Rayleigh waves, the depths are determined from the moment tensor inversion and fault inversion. The observed overtone Rayleigh waves are compared to the synthetic overtone seismograms to estimate the depth of faulting of these earthquakes. The depths obtained from overtone Rayleigh waves are consistent with the depths determined from fundamental Rayleigh waves for the two earthquakes. Appendix B gives the observed seismograms of fundamental and overtone Rayleigh waves for eleven large earthquakes.

Water in silicate glasses

The speciation of water in a variety of hydrous silicate glasses, including simple and rhyolitic compositions, synthesized over a range of experimental conditions with up to 11 weight percent water has been determined using infrared spectroscopy. This technique has been calibrated with a series of standard glasses and provides a precise and accurate method for determining the concentrations of molecular water and hydroxyl groups in these glasses.

For all the compositions studied, most of the water is dissolved as hydroxyl groups at total water contents less than 3-4 weight percent; at higher total water contents, molecular water becomes the dominant species. For total water contents above 3-4 weight percent, the amount of water dissolved as hydroxyl groups is approximately constant at about 2 weight percent and additional water is incorporated as molecular water. Although there are small but measurable differences in the ratio of molecular water to hydroxyl groups at a given total water content among these silicate glasses, the speciation of water is similar over this range of composition. The trends in the concentrations of the H-bearing species in the hydrous glasses included in this study are similar to those observed in other silicate glasses using either infrared or NMR spectroscopy.

The effects of pressure and temperature on the speciation of water in albitic glasses have been investigated. The ratio of molecular water to hydroxyl groups at a given total water content is independent of the pressure and temperature of equilibration for albitic glasses synthesized in rapidly quenching piston cylinder apparatus at temperatures greater than 1000°C and pressures greater than 8 kbar. For hydrous glasses quenched from melts cooled at slower rates (i.e., in internally heated or in air-quench cold seal pressure vessels), there is an increase in the ratio of molecular water to hydroxyl group content that probably reflects reequilibration of the melt to lower temperatures during slow cooling.

Molecular water and hydroxyl group concentrations in glasses provide information on the dissolution mechanisms of water in silicate liquids. Several mixing models involving homogeneous equilibria of the form H_2O + O = 20H among melt species have been explored for albitic melts. These models can account for the measured species concentrations if the effects of non-ideal behavior or mixing of polymerized units are included, or by allowing for the presence of several different types of anhydrous species.

A thermodynamic model for hydrous albitic melts has been developed based on the assumption that the activity of water in the melt is equal to the mole fraction of molecular water determined by infrared spectroscopy. This model can account for the position of the watersaturated solidus of crystalline albite, the pressure and temperature dependence of the solubility of water in albitic melt, and the volumes of hydrous albitic melts. To the extent that it is successful, this approach provides a direct link between measured species concentrations in hydrous albitic glasses and the macroscopic thermodynamic properties of the albite-water system.

The approach taken in modelling the thermodynamics of hydrous albitic melts has been generalized to other silicate compositions. Spectroscopic measurements of species concentrations in rhyolitic and simple silicate glasses quenched from melts equilibrated with water vapor provide important constraints on the thermodynamic properties of these melt-water systems. In particular, the assumption that the activity of water is equal to the mole fraction of molecular water has been tested in detail and shown to be a valid approximation for a range of hydrous silicate melts and the partial molar volume of water in these systems has been constrained. Thus, the results of this study provide a useful thermodynamic description of hydrous melts that can be readily applied to other melt-water systems for which spectroscopic measurements of the H-bearing species are available.

Invariants, Lie-Bäcklund operators and Bäcklund transformations

This thesis is mainly concerned with the application of groups of transformations to differential equations and in particular with the connection between the group structure of a given equation and the existence of exact solutions and conservation laws. In this respect the Lie-Bäcklund groups of tangent transformations, particular cases of which are the Lie tangent and the Lie point groups, are extensively used.

In Chapter I we first review the classical results of Lie, Bäcklund and Bianchi as well as the more recent ones due mainly to Ovsjannikov. We then concentrate on the Lie-Bäcklund groups (or more precisely on the corresponding Lie-Bäcklund operators), as introduced by Ibragimov and Anderson, and prove some lemmas about them which are useful for the following chapters. Finally we introduce the concept of a conditionally admissible operator (as opposed to an admissible one) and show how this can be used to generate exact solutions.

In Chapter II we establish the group nature of all separable solutions and conserved quantities in classical mechanics by analyzing the group structure of the Hamilton-Jacobi equation. It is shown that consideration of only Lie point groups is insufficient. For this purpose a special type of Lie-Bäcklund groups, those equivalent to Lie tangent groups, is used. It is also shown how these generalized groups induce Lie point groups on Hamilton's equations. The generalization of the above results to any first order equation, where the dependent variable does not appear explicitly, is obvious. In the second part of this chapter we investigate admissible operators (or equivalently constants of motion) of the Hamilton-Jacobi equation with polynornial dependence on the momenta. The form of the most general constant of motion linear, quadratic and cubic in the momenta is explicitly found. Emphasis is given to the quadratic case, where the particular case of a fixed (say zero) energy state is also considered; it is shown that in the latter case additional symmetries may appear. Finally, some potentials of physical interest admitting higher symmetries are considered. These include potentials due to two centers and limiting cases thereof. The most general two-center potential admitting a quadratic constant of motion is obtained, as well as the corresponding invariant. Also some new cubic invariants are found.

In Chapter III we first establish the group nature of all separable solutions of any linear, homogeneous equation. We then concentrate on the Schrodinger equation and look for an algorithm which generates a quantum invariant from a classical one. The problem of an isomorphism between functions in classical observables and quantum observables is studied concretely and constructively. For functions at most quadratic in the momenta an isomorphism is possible which agrees with Weyl' s transform and which takes invariants into invariants. It is not possible to extend the isomorphism indefinitely. The requirement that an invariant goes into an invariant may necessitate variants of Weyl' s transform. This is illustrated for the case of cubic invariants. Finally, the case of a specific value of energy is considered; in this case Weyl's transform does not yield an isomorphism even for the quadratic case. However, for this case a correspondence mapping a classical invariant to a quantum orie is explicitly found.

Chapters IV and V are concerned with the general group structure of evolution equations. In Chapter IV we establish a one to one correspondence between admissible Lie-Bäcklund operators of evolution equations (derivable from a variational principle) and conservation laws of these equations. This correspondence takes the form of a simple algorithm.

In Chapter V we first establish the group nature of all Bäcklund transformations (BT) by proving that any solution generated by a BT is invariant under the action of some conditionally admissible operator. We then use an algorithm based on invariance criteria to rederive many known BT and to derive some new ones. Finally, we propose a generalization of BT which, among other advantages, clarifies the connection between the wave-train solution and a BT in the sense that, a BT may be thought of as a variation of parameters of some. special case of the wave-train solution (usually the solitary wave one). Some open problems are indicated.

Most of the material of Chapters II and III is contained in [I], [II], [III] and [IV] and the first part of Chapter V in [V].

Attempts to Synthesize Cyclic Group 8 Metallaesters

In studying a proposed carbon monoxide reduction scheme an attempt has been made to synthesize bifunctional group 8 transition metal carbonyl complexes containing intramolecular nucleophiles. The incorporation of alkoxide nucleophiles through cyclopentadienyl ligands was hoped to encourage attack on carbonyl ligands thereby forming cyclic metallaesters. The attempts to synthesize these substituted cyclopentadienyl group 8 transition metal complexes have thus far been unsuccessful.