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.

Superionic Noble Metal Chalcogenide Thermoelectrics

Measurements and modeling of Cu₂Se, Ag₂Se, and Cu₂S show that superionic conductors have great potential as thermoelectric materials. Cu₂Se and Ag₂Se are predicted to reach a zT of 1.2 at room temperature if their carrier concentrations can be reduced, and Cu-vacancy doped Cu₂S reaches a maximum zT of 1.7 at 1000 K. Te-doped Ag₂Se achieves a zT of 1.2 at 520 K, and could reach a zT of 1.7 if its carrier concentration could be reduced. However, superionic conductors tend to have high carrier concentrations due to the presence of metal defects. The carrier concentration has been found to be difficult to reduce by altering the defect concentration, therefore materials that are underdoped relative to the optimum carrier concentration are easier to optimize. The results of Te-doping of Ag₂Se show that reducing the carrier concentration is possible by reducing the maximum Fermi level in the material.

Two new methods for analyzing thermoelectric transport data were developed. The first involves scaling the temperature-dependent transport data according to the temperature dependences expected of a single parabolic band model and using all of the scaled data to perform a single parabolic band analysis, instead of being restricted to using one data point per sample at a fixed temperature. This allows for a more efficient use of the transport data. The second involves scaling only the Seebeck coefficient and electrical conductivity. This allows for an estimate of the quality factor (and therefore the maximum zT in the material) without using Hall effect data, which are not always available due to time and budget constraints and are difficult to obtain in high-resistivity materials. Methods for solving the coherent potential approximation effective medium equations were developed in conjunction with measurements of the resistivity tensor elements of composite materials. This allows the electrical conductivity and mobility of each phase in the composite to be determined from measurements of the bulk. This points out a new method for measuring the pure-phase electrical properties in impure materials, for measuring the electrical properties of unknown phases in composites, and for quantifying the effects of quantum interactions in composites.

On the Cesari fixed point method in a Banach space

In a paper published in 1961, L. Cesari [1] introduces a method which extends certain earlier existence theorems of Cesari and Hale ([2] to [6]) for perturbation problems to strictly nonlinear problems. Various authors ([1], [7] to [15]) have now applied this method to nonlinear ordinary and partial differential equations. The basic idea of the method is to use the contraction principle to reduce an infinite-dimensional fixed point problem to a finite-dimensional problem which may be attacked using the methods of fixed point indexes.

The following is my formulation of the Cesari fixed point method:

Let B be a Banach space and let S be a finite-dimensional linear subspace of B. Let P be a projection of B onto S and suppose Г≤B such that pГ is compact and such that for every x in PГ, P^-1x∩Г is closed. Let W be a continuous mapping from Г into B. The Cesari method gives sufficient conditions for the existence of a fixed point of W in Г.

Let I denote the identity mapping in B. Clearly y = Wy for some y in Г if and only if both of the following conditions hold:

(i) Py = PWy.

(ii) y = (P + (I - P)W)y.

Definition. The Cesari fixed paint method applies to (Г, W, P) if and only if the following three conditions are satisfied:

(1) For each x in PГ, P + (I - P)W is a contraction from P^-1x∩Г into itself. Let y(x) be that element (uniqueness follows from the contraction principle) of P^-1x∩Г which satisfies the equation y(x) = Py(x) + (I-P)Wy(x).

(2) The function y just defined is continuous from PГ into B.

(3) There are no fixed points of PWy on the boundary of PГ, so that the (finite- dimensional) fixed point index i(PWy, int PГ) is defined.

Definition. If the Cesari fixed point method applies to (Г, W, P) then define i(Г, W, P) to be the index i(PWy, int PГ).

The three theorems of this thesis can now be easily stated.

Theorem 1 (Cesari). If i(Г, W, P) is defined and i(Г, W, P) ≠0, then there is a fixed point of W in Г.

Theorem 2. Let the Cesari fixed point method apply to both (Г, W, P₁) and (Г, W, P₂). Assume that P₂P₁=P₁P₂=P₁ and assume that either of the following two conditions holds:

(1) For every b in B and every z in the range of P₂, we have that ‖b=P₂b‖ ≤ ‖b-z‖

(2)P₂Г is convex.

Then i(Г, W, P₁) = i(Г, W, P₂).

Theorem 3. If Ω is a bounded open set and W is a compact operator defined on Ω so that the (infinite-dimensional) Leray-Schauder index i_LS(W, Ω) is defined, and if the Cesari fixed point method applies to (Ω, W, P), then i(Ω, W, P) = i_LS(W, Ω).

Theorems 2 and 3 are proved using mainly a homotopy theorem and a reduction theorem for the finite-dimensional and the Leray-Schauder indexes. These and other properties of indexes will be listed before the theorem in which they are used.