Thesis (Ph. D.)--University of Wisconsin--Madison, 1956. / Typescript. Abstracted in Dissertation abstracts, v. 16 (1956) no. 4, p. 784. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 122-126).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1958. / Typescript. Abstracted in Dissertation abstracts, v. 19 (1958) no. 4, p. 654. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 84-89).

This Thesis describes the synthesis and characterisation of titanium hydrazido(2-) complexes and their reactivity towards unsaturated molecules. Exploration of the bonding in titanium hydrazido(2-) complexes is performed through structural and computational studies. <strong>Chapter 1</strong> introduces current Group 4 hydrazido chemistry and describes its relevance with comparison to Group 4 imido and mid/late metal hydrazido examples. <strong>Chapter 2</strong> describes the synthesis and characterisation of new titanium hydrazido(2-) half-sandwich complexes. A general route to new titanium hydrazido(2-) chemistry is described and suppression of dimerisation pathways common to Group 4 alkyl hydrazido(2-) chemistry is investigated. <strong>Chapter 3</strong> describes the synthesis, bonding and preliminary reaction chemistry of a new titanium hydrazido(2-) sandwich complex. Through structural and computational techniques, the bonding in the sandwich complex Cp₂Ti(NNPh₂)(py) (14) is explored and the implications to the reactivity of this complex considered. <strong>Chapter 4</strong> describes the synthesis of new titanium hydrazido(2-) synthons which is extended to the synthesis of new titanium hydrazido(2-) complexes with diamide-amine type ligands. The bonding of the hydrazido(2-) ligand is explored through structural and computational study of these complexes. <strong>Chapter 5</strong> describes the novel reaction chemistry of a diamide-pyridyl titanium hydrazido(2-) complex Ti(N₂N^py)(NNPh₂)(py) (23). Novel reactivity of both the Ti=N_&alpha; and N_&alpha;-N_&beta; bonds is presented with the mechanisms of some of these transformations probed by density functional theory (DFT) calculations. <strong>Chapter 6</strong> presents full experimental procedures and characterising data for the new complexes reported. <strong>CD Appendix</strong> contains .cif files for all new crystallographically characterised complexes described.

Nitrogen-containing molecules are ubiquitous in both natural products and pharmaceutical drugs, thus an efficient method for the formation of these motifs is of great importance. Hydroamination, that is the addition of an N-H bond across an unsaturated carbon-carbon bond of an alkene or alkyne, stands out as a potential approach to obtain such molecules. To date, most research in this area relies on transition-metal catalysis to enable such reactivity. In efforts directed towards metal-free alternatives, we have developed a simple, metal-free hydroamination of alkenes using hydrazides. Further investigation into the corresponding reactivity of alkynes with hydrazides has provided access to novel azomethine imine products. In Chapter 2, expansion of the substrate scope with respect to the intramolecular hydroamination of alkenes using hydrazides, as well as studies directed towards elucidation of the mechanism of this reaction will be presented. The intramolecular hydroamination of alkynes using hydrazides and methods to access and isolate the azomethine imine products formed will be discussed in Chapter 3.

Nitrogen-containing molecules are ubiquitous in both natural products and pharmaceutical drugs, thus an efficient method for the formation of these motifs is of great importance. Hydroamination, that is the addition of an N-H bond across an unsaturated carbon-carbon bond of an alkene or alkyne, stands out as a potential approach to obtain such molecules. To date, most research in this area relies on transition-metal catalysis to enable such reactivity. In efforts directed towards metal-free alternatives, we have developed a simple, metal-free hydroamination of alkenes using hydrazides. Further investigation into the corresponding reactivity of alkynes with hydrazides has provided access to novel azomethine imine products. In Chapter 2, expansion of the substrate scope with respect to the intramolecular hydroamination of alkenes using hydrazides, as well as studies directed towards elucidation of the mechanism of this reaction will be presented. The intramolecular hydroamination of alkynes using hydrazides and methods to access and isolate the azomethine imine products formed will be discussed in Chapter 3.

No description available.

Nitrogen-containing molecules are ubiquitous in both natural products and pharmaceutical drugs, thus an efficient method for the formation of these motifs is of great importance. Hydroamination, that is the addition of an N-H bond across an unsaturated carbon-carbon bond of an alkene or alkyne, stands out as a potential approach to obtain such molecules. To date, most research in this area relies on transition-metal catalysis to enable such reactivity. In efforts directed towards metal-free alternatives, we have developed a simple, metal-free hydroamination of alkenes using hydrazides. Further investigation into the corresponding reactivity of alkynes with hydrazides has provided access to novel azomethine imine products. In Chapter 2, expansion of the substrate scope with respect to the intramolecular hydroamination of alkenes using hydrazides, as well as studies directed towards elucidation of the mechanism of this reaction will be presented. The intramolecular hydroamination of alkynes using hydrazides and methods to access and isolate the azomethine imine products formed will be discussed in Chapter 3.

Zugl.: Braunschweig, Techn. Univ., Diss., 2007

Universiẗat, Diss., 2002--Dortmund.

Nitrogen-containing molecules are ubiquitous in both natural products and pharmaceutical drugs, thus an efficient method for the formation of these motifs is of great importance. Hydroamination, that is the addition of an N-H bond across an unsaturated carbon-carbon bond of an alkene or alkyne, stands out as a potential approach to obtain such molecules. To date, most research in this area relies on transition-metal catalysis to enable such reactivity. In efforts directed towards metal-free alternatives, we have developed a simple, metal-free hydroamination of alkenes using hydrazides. Further investigation into the corresponding reactivity of alkynes with hydrazides has provided access to novel azomethine imine products. In Chapter 2, expansion of the substrate scope with respect to the intramolecular hydroamination of alkenes using hydrazides, as well as studies directed towards elucidation of the mechanism of this reaction will be presented. The intramolecular hydroamination of alkynes using hydrazides and methods to access and isolate the azomethine imine products formed will be discussed in Chapter 3.