Reactivity of titanocene methylidene with metal halides, alkene sulfides, and alkene oxides

Titanocene metallacyclobutanes show a wide variety of reactivites with organic and inorganic reagents. Their reactions include methylene transfer to organic carbonyls, formation of enolates, electron transfer from activated alkyl chlorides, olefin metathesis, ring opening polymerization. Recently, preparations of heterobinuclear µ-methylene complexes were reported. In this thesis, mechanistic, synthetic, and structural studies of the heterobinuclear µ-methylene complexes will be described. Also, the reaction of titanocene methylidene trimethylphosphine complex with alkene sulfide and styrene sulfide will be presented.

Heterobinuclear µ-methylene-µ-methyl complexes C_(p2)Ti(µ-CH_2)( µ-CH_3)M(1,5-COD) have been prepared (M = Rh, Ir). X-ray crystallography showed that the methyl group of the complex was bonded to the rhodium and bridges to the titanium through an agostic bond. The ^(1)H,^(13)CNMR, IR spectra along with partial deuteration studies supported the structure in both solution and solid state. Activation of the agostic bond is demonstrated by the equilibration of the µ-CH_3 and µ-CH_2 groups. A nonlinear Arrhenius plot, an unusually large kinetic isotope effect (24(5)), and a large negative activation entropy (-64(3)eu) can be explained by the quantum-mechanical tunneling. Calculated rate constants with Bell-type barrier fitted well with the observed one. This equilibration was best explained by a 4e-4c mechanism (or σ bond metathesis) with the character of quantum-mechanical tunneling.

Heterobinuclear µ-methylene-µ-phenyl complexes were synthesized. Structural study of C_(p2)Ti(µ-CH_(2))(µ-p-Me_(2)NC_(6)H_(4))Rh(l,5-COD) showed that the two metal atoms are bridged by the methylene carbon and the ipso carbon of the p-N,N-dimethylarninophenyl group. The analogous structure of C_(p2))Ti(µ-CH_(2))(µ-o-MeOC_(6)H_(4))Rh(1,5-COD) has been verified by the differential NOE. The aromaticity of the phenyl group observed by ^(1)H NMR, was confirmed by the comparison of the C-C bond lengths in the crystallographic structure. The unusual downfield shifts of the ipso carbon in the ^(13)C NMR are assumed to be an indication of the interaction between the ipso carbon and electron-deficient titanium.

Titanium-platinum heterobinuclear µ-methylene complexes C_(p2)Ti(µ-CH_(2))(µ -X)Pt(Me)(PM_(2)Ph) have been prepared (X= Cl, Me). Structural studies indicate the following:(1) the Ti-CH2 bond possesses residual double bond character, (2) there is a dative Pt→Ti interaction which may be regarded as a π back donation from the platinum atom to the 'Ti=CH_(2)'' group, and (3) the µ-CH_3 group is bound to the titanium atom through a three-center, two-electron agostic bond.

Titanocene (η^(2)-thioformaldehyde)•PMe_3 was prepared from C_(p2)Ti=CH_(2)•PMe_3 and sulfur-containing organic compounds (e.g. alkene sulfide, triphenylphosphine sulfide) including elemental sulfur. Mechanistic studies utilizing trans-styrene sulfide-d_1 suggested the stepwise reaction to explain equimolar mixture of trans- and cis-styrene-d_1 as by-products. The product reacted with methyl iodide to produce cationic titanocene (η_(2)-thiomethoxymethyl) complex. Complexes having less coordinating anion like BF_4 or BPh_4 could be obtained through metathesis. Together with structural analyses, the further reactivities of the complexes have been explored.

The complex C_(p2)TiOCH_(2)CH(Ph)CH_2 was prepared from the compound C_(p2)Ti=CH_(2)-PMe_3 and styrene oxide. The product was characterized with ^(1)H-^(1)H correlated 2-dimensional NMR, selective decoupling of ^(1)H NMR, and differential NOE. Stereospecificity of deuterium in the product was lost when trans-styrene oxide-d_1 was allowed to react. Relative rates of the reaction were measured with varying substituents on the phenyl ring. Better linearity (r = -0.98, p^(+) = -0.79) was observed with σ_(p)^(+)than σ(r = -0.87, p = -1.26). The small magnitude of p^+ value and stereospecificity loss during the formation of product were best explained by the generation of biradicals, but partial generation of charge cannot be excluded. Carbonylation of the product followed by exposure to iodine yields the corresponding β-phenyl γ-lactone.

Experiments with a laser interferometric gravitational wave antenna

Sources and effects of astrophysical gravitational radiation are explained briefly to motivate discussion of the Caltech 40 meter antenna, which employs laser interferometry to monitor proper distances between inertial test masses. Practical considerations in construction of the apparatus are described. Redesign of test mass systems has resulted in a reduction of noise from internal mass vibrations by up to two orders of magnitude at some frequencies. A laser frequency stabilization system was developed which corrects the frequency of an argon ion laser to a residual fluctuation level bounded by the spectral density √s_v(f) ≤ 60µHz/√Hz, at fluctuation frequencies near 1.2 kHz. These and other improvements have contributed to reducing the spectral density of equivalent gravitational wave strain noise to √s_h(f)≈10^(-19)/√ Hz at these frequencies.

Finally, observations made with the antenna in February and March of 1987 are described. Kilohertz-band gravitational waves produced by the remnant of the recent supernova are shown to be theoretically unlikely at the strength required for confident detection in this antenna (then operating at poorer sensitivity than that quoted above). A search for periodic waves in the recorded data, comprising Fourier analysis of four 105-second samples of the antenna strain signal, was used to place new upper limits on periodic gravitational radiation at frequencies between 305 Hz and 5 kHz. In particular, continuous waves of any polarization are ruled out above strain amplitudes of 1.2 x 10^(-18) R.M.S. for waves emanating from the direction of the supernova, and 6.2 x 10^(-19) R.M.S. for waves emanating from the galactic center, between 1.5 and 4 kilohertz. Between 305 Hz and 5kHz no strains greater than 1.2 x 10^(-17) R.M.S. were detected from either direction. Limitations of the analysis and potential improvements are discussed, as are prospects for future searches.

Studies of molecular bonding, interactions and decomposition reactions on the (001) surface of ruthenium

The interactions of N₂, formic acid and acetone on the Ru(001) surface are studied using thermal desorption mass spectrometry (TDMS), electron energy loss spectroscopy (EELS), and computer modeling.

Low energy electron diffraction (LEED), EELS and TDMS were used to study chemisorption of N₂ on Ru(001). Adsorption at 75 K produces two desorption states. Adsorption at 95 K fills only the higher energy desorption state and produces a (√3 x √3)R30° LEED pattern. EEL spectra indicate both desorption states are populated by N₂ molecules bonded "on-top" of Ru atoms.

Monte Carlo simulation results are presented on Ru(001) using a kinetic lattice gas model with precursor mediated adsorption, desorption and migration. The model gives good agreement with experimental data. The island growth rate was computed using the same model and is well fit by R(t)^m - R(t₀)^m = At, with m approximately 8. The island size was determined from the width of the superlattice diffraction feature.

The techniques, algorithms and computer programs used for simulations are documented. Coordinate schemes for indexing sites on a 2-D hexagonal lattice, programs for simulation of adsorption and desorption, techniques for analysis of ordering, and computer graphics routines are discussed.

The adsorption of formic acid on Ru(001) has been studied by EELS and TDMS. Large exposures produce a molecular multilayer species. A monodentate formate, bidentate formate, and a hydroxyl species are stable intermediates in formic acid decomposition. The monodentate formate species is converted to the bidentate species by heating. Formic acid decomposition products are CO₂, CO, H₂, H₂O and oxygen adatoms. The ratio of desorbed CO with respect to CO₂ increases both with slower heating rates and with lower coverages.

The existence of two different forms of adsorbed acetone, side-on, bonded through the oxygen and acyl carbon, and end-on, bonded through the oxygen, have been verified by EELS. On Pt(111), only the end-on species is observed. On dean Ru(001) and p(2 x 2)O precovered Ru(001), both forms coexist. The side-on species is dominant on clean Ru(001), while O stabilizes the end-on form. The end-on form desorbs molecularly. Bonding geometry stability is explained by surface Lewis acidity and by comparison to organometallic coordination complexes.

Regional variations in upper mantle structure beneath North America

Several types of seismological data, including surface wave group and phase velocities, travel times from large explosions, and teleseismic travel time anomalies, have indicated that there are significant regional variations in the upper few hundred kilometers of the mantle beneath continental areas. Body wave travel times and amplitudes from large chemical and nuclear explosions are used in this study to delineate the details of these variations beneath North America.

As a preliminary step in this study, theoretical P wave travel times, apparent velocities, and amplitudes have been calculated for a number of proposed upper mantle models, those of Gutenberg, Jeffreys, Lehman, and Lukk and Nersesov. These quantities have been calculated for both P and S waves for model CIT11GB, which is derived from surface wave dispersion data. First arrival times for all the models except that of Lukk and Nersesov are in close agreement, but the travel time curves for later arrivals are both qualitatively and quantitatively very different. For model CIT11GB, there are two large, overlapping regions of triplication of the travel time curve, produced by regions of rapid velocity increase near depths of 400 and 600 km. Throughout the distance range from 10 to 40 degrees, the later arrivals produced by these discontinuities have larger amplitudes than the first arrivals. The amplitudes of body waves, in fact, are extremely sensitive to small variations in the velocity structure, and provide a powerful tool for studying structural details.

Most of eastern North America, including the Canadian Shield has a Pn velocity of about 8.1 km/sec, with a nearly abrupt increase in compressional velocity by ~ 0.3 km/sec near at a depth varying regionally between 60 and 90 km. Variations in the structure of this part of the mantle are significant even within the Canadian Shield. The low-velocity zone is a minor feature in eastern North America and is subject to pronounced regional variations. It is 30 to 50 km thick, and occurs somewhere in the depth range from 80 to 160 km. The velocity decrease is less than 0.2 km/sec.

Consideration of the absolute amplitudes indicates that the attenuation due to anelasticity is negligible for 2 hz waves in the upper 200 km along the southeastern and southwestern margins of the Canadian Shield. For compressional waves the average Q for this region is > 3000. The amplitudes also indicate that the velocity gradient is at least 2 x 10^-3 both above and below the low-velocity zone, implying that the temperature gradient is < 4.8°C/km if the regions are chemically homogeneous.

In western North America, the low-velocity zone is a pronounced feature, extending to the base of the crust and having minimum velocities of 7.7 to 7.8 km/sec. Beneath the Colorado Plateau and Southern Rocky Mountains provinces, there is a rapid velocity increase of about 0.3 km/sec, similar to that observed in eastern North America, but near a depth of 100 km.

Complicated travel time curves observed on profiles with stations in both eastern and western North America can be explained in detail by a model taking into account the lateral variations in the structure of the low-velocity zone. These variations involve primarily the velocity within the zone and the depth to the top of the zone; the depth to the bottom is, for both regions, between 140 and 160 km.

The depth to the transition zone near 400 km also varies regionally, by about 30-40 km. These differences imply variations of 250 °C in the temperature or 6 % in the iron content of the mantle, if the phase transformation of olivine to the spinel structure is assumed responsible. The structural variations at this depth are not correlated with those at shallower depths, and follow no obvious simple pattern.

The computer programs used in this study are described in the Appendices. The program TTINV (Appendix IV) fits spherically symmetric earth models to observed travel time data. The method, described in Appendix III, resembles conventional least-square fitting, using partial derivatives of the travel time with respect to the model parameters to perturb an initial model. The usual ill-conditioned nature of least-squares techniques is avoided by a technique which minimizes both the travel time residuals and the model perturbations.

Spherically symmetric earth models, however, have been found inadequate to explain most of the observed travel times in this study. TVT4, a computer program that performs ray theory calculations for a laterally inhomogeneous earth model, is described in Appendix II. Appendix I gives a derivation of seismic ray theory for an arbitrarily inhomogeneous earth model.

Enzyme induction in Neurospora crassa

I. Studies on Nicotinamide Adenine Dinucleotide Glycohydrase (NADase)

NADase, like tyrosinase and L-amino acid oxidase, is not present in two day old cultures of wild type Neurospora, but it is coinduced with those two enzymes during starvation in phosphate buffer. The induction of NADase, like tyrosinase, is inhibited by puromycin. The induction of all three enzymes is inhibited by actinomycin D. These results suggest that NADase is synthesized de novo during induction as has been shown directly for tyrosinase. NADase induction differs in being inhibited by certain amino acids.

The tyrosinaseless mutant ty-1 contains a non-dialyzable, heat labile inhibitor of NADase. A new mutant, P110A, synthesizes NADase and L-amino acid oxidase while growing. A second strain, pe, fl;cot, makes NADase while growing. Both strains can be induced to make the other enzymes. These two strains prove that the control of these three enzymes is divisible. The strain P110A makes NADase even when grown in the presence of Tween 80. The synthesis of both NADase and L-amino acid oxidase by P110A is suppressed by complete medium. The theory of control of the synthesis of the enzymes is discussed.

II. Studies with EDTA

Neurospora tyrosinase contains copper but, unlike other phenol oxidases, this copper has never been removed reversibly. It was thought that the apo-enzyme might be made in vivo in the absence of copper. Therefore cultures were treated with EDTA to remove copper before the enzyme was induced. Although no apo-tyrosinase was detected, new information on the induction process was obtained.

A treatment of Neurospora with 0.5% EDTA pH 7, inhibits the subsequent induction during starvation in phosphate buffer of tyrosinase, L-amino acid oxidase and NADase. The inhibition of tyrosinase and L-amino acid oxidase induction is completely reversed by adding 5 x 10^-5M CaCl₂, 5 x 10^-4M CuSO₄, and a mixture of L-amino acids (2 x 10^-3M each) to the buffer. Tyrosinase induction is also fully restored by 5 x 10^-4M CaCl₂ and amino acids. As yet NADase has been only partially restored.

The copper probably acts by sequestering EDTA left in the mycelium and may be replaced by nickel. The EDTA apparently removes some calcium from the mycelium, which the added calcium replaces. Magnesium cannot replace calcium. The amino acids probably replace endogenous amino acids lost to the buffer after the EDTA treatment.

The EDTA treatment also increases permeability, thereby increasing the sensitivity of induction to inhibition by actinomycin D and allowing cell contents to be lost to the induction buffer. EDTA treatment also inhibits the uptake of exogenous amino acids and their incorporation into proteins.

The lag period that precedes the first appearance of tyrosinase is demonstrated to be a separate dynamic phase of induction. It requires oxygen. It is inhibited by EDTA, but can be completed after EDTA treatment in the presence of 5 x 10^-5M CaCl₂ alone, although no tyrosinase is synthesized under these conditions.

The time course of induction has an early exponential phase suggesting an autocatalytic mechanism of induction.

The mode of action of EDTA, the process of induction and the kinetics of induction are discussed.

On the distribution of the signs of the conjugates of the cyclotomic units in the maximal real subfield of the qth cyclotomic field, q A prime

Let F = Ǫ(ζ + ζ ^–1) be the maximal real subfield of the cyclotomic field Ǫ(ζ) where ζ is a primitive qth root of unity and q is an odd rational prime. The numbers u₁=-1, u_k=(ζ^k-ζ^-k)/(ζ-ζ^-1), k=2,…,p, p=(q-1)/2, are units in F and are called the cyclotomic units. In this thesis the sign distribution of the conjugates in F of the cyclotomic units is studied.

Let G(F/Ǫ) denote the Galoi's group of F over Ǫ, and let V denote the units in F. For each σϵ G(F/Ǫ) and μϵV define a mapping sgn_σ: V→GF(2) by sgn_σ(μ) = 1 iff σ(μ) ˂ 0 and sgn_σ(μ) = 0 iff σ(μ) ˃ 0. Let {σ₁, ... , σ_p} be a fixed ordering of G(F/Ǫ). The matrix M_q=(sgn_σj(v_i) ) , i, j = 1, ... , p is called the matrix of cyclotomic signatures. The rank of this matrix determines the sign distribution of the conjugates of the cyclotomic units. The matrix of cyclotomic signatures is associated with an ideal in the ring GF(2) [x] / (x^p+ 1) in such a way that the rank of the matrix equals the GF(2)-dimension of the ideal. It is shown that if p = (q-1)/ 2 is a prime and if 2 is a primitive root mod p, then M_q is non-singular. Also let p be arbitrary, let ℓ be a primitive root mod q and let L = {i | 0 ≤ i ≤ p-1, the least positive residue of defined by ℓⁱ mod q is greater than p}. Let H_q(x) ϵ GF(2)[x] be defined by H_q(x) = g. c. d. ((Σ xⁱ/I ϵ L) (x+1) + 1, x^p + 1). It is shown that the rank of M_q equals the difference p - degree H_q(x).

Further results are obtained by using the reciprocity theorem of class field theory. The reciprocity maps for a certain abelian extension of F and for the infinite primes in F are associated with the signs of conjugates. The product formula for the reciprocity maps is used to associate the signs of conjugates with the reciprocity maps at the primes which lie above (2). The case when (2) is a prime in F is studied in detail. Let T denote the group of totally positive units in F. Let U be the group generated by the cyclotomic units. Assume that (2) is a prime in F and that p is odd. Let F₍₂₎ denote the completion of F at (2) and let V₍₂₎ denote the units in F₍₂₎. The following statements are shown to be equivalent. 1) The matrix of cyclotomic signatures is non-singular. 2) U∩T = U². 3) U∩F²₍₂₎ = U². 4) V₍₂₎/ V₍₂₎² = ˂v₁ V₍₂₎²˃ ʘ…ʘ˂v_p V₍₂₎²˃ ʘ ˂3V₍₂₎²˃.

The rank of M_q was computed for 5≤q≤929 and the results appear in tables. On the basis of these results and additional calculations the following conjecture is made: If q and p = (q -1)/ 2 are both primes, then M_q is non-singular.

High frequency wave propagation in the earth: theory and observation

The wave-theoretical analysis of acoustic and elastic waves refracted by a spherical boundary across which both velocity and density increase abruptly and thence either increase or decrease continuously with depth is formulated in terms of the general problem of waves generated at a steady point source and scattered by a radially heterogeneous spherical body. A displacement potential representation is used for the elastic problem that results in high frequency decoupling of P-SV motion in a spherically symmetric, radially heterogeneous medium. Through the application of an earth-flattening transformation on the radial solution and the Watson transform on the sum over eigenfunctions, the solution to the spherical problem for high frequencies is expressed as a Weyl integral for the corresponding half-space problem in which the effect of boundary curvature maps into an effective positive velocity gradient. The results of both analytical and numerical evaluation of this integral can be summarized as follows for body waves in the crust and upper mantle:

1) In the special case of a critical velocity gradient (a gradient equal and opposite to the effective curvature gradient), the critically refracted wave reduces to the classical head wave for flat, homogeneous layers.

2) For gradients more negative than critical, the amplitude of the critically refracted wave decays more rapidly with distance than the classical head wave.

3) For positive, null, and gradients less negative than critical, the amplitude of the critically refracted wave decays less rapidly with distance than the classical head wave, and at sufficiently large distances, the refracted wave can be adequately described in terms of ray-theoretical diving waves. At intermediate distances from the critical point, the spectral amplitude of the refracted wave is scalloped due to multiple diving wave interference.

These theoretical results applied to published amplitude data for P-waves refracted by the major crustal and upper mantle horizons (the Pg, P*, and Pn travel-time branches) suggest that the 'granitic' upper crust, the 'basaltic' lower crust, and the mantle lid all have negative or near-critical velocity gradients in the tectonically active western United States. On the other hand, the corresponding horizons in the stable eastern United States appear to have null or slightly positive velocity gradients. The distribution of negative and positive velocity gradients correlates closely with high heat flow in tectonic regions and normal heat flow in stable regions. The velocity gradients inferred from the amplitude data are generally consistent with those inferred from ultrasonic measurements of the effects of temperature and pressure on crustal and mantle rocks and probable geothermal gradients. A notable exception is the strong positive velocity gradient in the mantle lid beneath the eastern United States (2 x 10^-3 sec^-1), which appears to require a compositional gradient to counter the effect of even a small geothermal gradient.

New seismic-refraction data were recorded along a 800 km profile extending due south from the Canadian border across the Columbia Plateau into eastern Oregon. The source for the seismic waves was a series of 20 high-energy chemical explosions detonated by the Canadian government in Greenbush Lake, British Columbia. The first arrivals recorded along this profile are on the Pn travel-time branch. In northern Washington and central Oregon their travel time is described by T = Δ/8.0 + 7.7 sec, but in the Columbia Plateau the Pn arrivals are as much as 0.9 sec early with respect to this line. An interpretation of these Pn arrivals together with later crustal arrivals suggest that the crust under the Columbia Plateau is thinner by about 10 km and has a higher average P-wave velocity than the 35-km-thick, 62-km/sec crust under the granitic-metamorphic terrain of northern Washington. A tentative interpretation of later arrivals recorded beyond 500 km from the shots suggests that a thin 8.4-km/sec horizon may be present in the upper mantle beneath the Columbia Plateau and that this horizon may form the lid to a pronounced low-velocity zone extending to a depth of about 140 km.

Part I: Total yield measurements for the ^(21)Ne(α,n)^)(24)Mg reaction. Part II: A study of the ^(12)C(He,p)^(14)N reaction

PART I

The total cross-section for the reaction ²¹Ne(α, n)²⁴Mg has been measured in the energy range 1.49 Mev ≤ E_cm ≤ 2.6 Mev. The cross-section factor, S(O), for this reaction has been determined, by means of an optical model calculation, to be in the range 1.52 x 10¹² mb-Mev to 2.67 x 10¹² mb-Mev, for interaction radii in the range 5.0 fm to 6.6 fm. With S(O) ≈ 2 x 10¹² mb-Mev, the reaction ²¹Ne(α, n)²⁴Mg can produce a large enough neutron flux to be a significant astrophysical source of neutrons.

PART II

The reaction¹²C(³He, p)¹⁴N has been studied over the energy range 12 Mev ≤ E_lab ≤ 18 Mev. Angular distributions of the proton groups leading to the lowest seven levels in ¹⁴N were obtained.

Distorted wave calculations, based on two-nucleon transfer theory, were performed, and were found to be reliable for obtaining the value of the orbital angular momentum transferred. The present work shows that such calculations do not yield unambiguous values for the spectroscopic factors.