Thesis (Ph. D.)--University of Wisconsin--Madison, 1932. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Master)--İzmir Institute of Technology, İzmir, 2005 / Includes bibliographical references (leaves 35-37).

There is a continued interest in the properties of arsenic thiolate compounds for both industrial and biological uses. Recent discoveries in the medicinal properties of such compounds have resulted in a sustained need for the synthesis of new dithiarsolane compounds for research as anti-leukemic compounds. Close analogues of the 2-halo arsenic dithiolates, namely those with an arsenic-carbon bond instead of an arsenic-halide bond, have recently been shown to have some efficacy towards leukemia cells. Based on the hydrolytic character and the active role of glutathione with arsenic in vivo, the compounds reported here may also have such activity. Arsenic compounds have demonstrated biological activity in the literature, thus the hypothesis of this thesis is cyclized arsenic thiolates can be synthesized with the appropriate characteristics as to be potentially useful medicinal agents as well as provide new structural and reaction information. A series of arsenic and antimony di- and trithiolates has been synthesized and characterized. Those compounds include 2-chloro-1,3,2-dithiarsolane, 2-bromo- 1,3,2-dithiarsolane, 2-iodo-1,3,2-dithiarsolane, 2-chloro-1,3,2-dithiarsenane, 2-bromo- 1,3,2-dithiarsenane, 2-iodo-1,3,2-dithiarsenane, 3-chloro-4H,7H-5,6-benz-1,3,2- dithiarsepine, 2-chloro-benzo-1,3,2-dithiarsole, 1,2-bis-dithiarsolan-2-ylmercapto-ethane, tris-(pentafluorophenylthio)-arsen, bis(2-(1,3,2-benzodithiarsol-2ylsulfanyl)- benzenesulfide), 2-chloro-benzo-1,3,2-dithiastibole, and bis(2-(1,3,2-benzodithistibol)- 1,2-benzenedithiol. Elucidation of the pH characteristics of arsenic dithiolates within the human toxicity reaction pathway is an area of interest. It has been shown that the aqueous arsenic dithiolate stability depends on the size of the ring. 2-Chloro-1,3,2-dithiarsolane has been shown to be somewhat stable at both low and high pH as well as neutral pH. 1,2-bis- Dithiarsolan-2-ylmercapto-ethane is completely stable in a neutral aqueous solution. Glutathione does not permanently bind to arsenic even in overwhelming excess. In particular, these fully characterized compounds determine how reactive the AsS and AsCl linkages are under environmental and biological conditions, and provide a source of new reagents to examine in medical applications. Future applications may include the incorporation of the reported compounds in filtration and remediation technologies with further modification.

Donor–acceptor complexes have been known for over a century and enjoy a long list of applications in chemistry. In this thesis, the dative interaction between phosphorus and its two heavier congeners, arsenic and antimony, are explored. Utilising peri-substitution atoms can be forced in close proximity to one another, resulting in a repulsive (nonbonding) interaction or an attractive (bonding) interaction. Hence, peri-substitution can be used to support traditionally ephemeral species. A range of phosphorus, arsenic and antimony containing peri-substituted compounds were synthesised and characterised using multi-nuclear NMR, mass spectrometry, elemental microanalysis and single crystal X-ray diffraction. The reduction of a peri-substituted dichloroarsine, led to the formation of a primary arsine, which underwent spontaneous elimination of hydrogen gas forming the first structurally characterised cyclic arsanylidene–σ⁴–phosphorane, the formation of which is essentially thermoneutral. With no sterically demanding groups shielding the arsenic atom, the reactivity and spectroscopic characteristics of this compound were explored through reactions with selected metal complexes. Reaction of the arsanylidene–phosphorane with a limited amount of oxygen reveals arsinidene–like reactivity via the formation of cycloarsines, supporting the formulation that the bonding can be described as a Lewis base–stabilised arsinidene R₃P→AsR. A series of phosphine–stibine and phosphine–stiborane peri-substituted acenaphthenes containing all permutations of pentavalent groups –SbCl[sub]nPh[sub](4-n) as well as trivalent groups –SbCl₂, –Sb(R)Cl, and –SbPh₂ (R = Ph, Mes), were synthesised and characterised by multi-nuclear NMR, MS, microanalysis and X-ray crystallography. The bonding in these species was studied by DFT computational methods. The P–Sb dative interactions range from strongly bonding to nonbonding as the Lewis acidity of the Sb acceptor is decreased. Unexpectedly, the phosphine–stiborane complexes represent the first examples of σ⁴P→σ⁶Sb structural motif. A study of unsymmetrical bis(phosphino)acenaphthenes showed the presence of a 3c–4e interaction, supported by the short P∙∙∙P distances and the large J[sub](PP) through-space couplings. Severely strained bis(sulfides) of the unsymmetrical phosphines experience pronounced displacements of the exocyclic peri-atoms. The resulting nonbonded intramolecular P∙∙∙P distances (ca. 4.05 Å) are among the largest ever reported peri-separations, independent of the heteroatoms involved. In addition, three metal complexes with square planar, tetrahedral and octahedral geometry are reported. In all three cases, the acenaphthene backbone is distorted to a greater extent than in the free bis(phosphine) but notably less than in the bis(sulfides).