Date of Award

1996

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

First Advisor

Drake, G.

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

The S-alkyltrithiocarbonate(thioxanthate) derivatives, $\rm Ph\sb3Ge\lbrack S\sb2CSR\rbrack,\ Ph\sb2Ge\lbrack S\sb2CSR\rbrack\sb2,\ Ph\sb2GeX\lbrack S\sb2CSR\rbrack,\ Me\sb3Ge\lbrack S\sb2CSR\rbrack\sb2,$ and $\rm Me\sb2Ge\lbrack S\sb2CSR\rbrack\sb2$, where R = Et, i-Pr, n-Pr and n-Bu, X = Cl and Br, have been synthesized by the metatheses of $\rm R\sb2GeX\sb2$ or $\rm R\sb3GeX$ with Na of $\rm KS\sb2CSR\sp\prime$, where R = Ph and Me, R$\sp\prime$ = Et, i-Pr, n-Pr and n-Bu, X = Cl and Br. The compounds were characterized by means of NMR, IR and Raman spectroscopy. The crystal structures of $\rm Ph\sb2Ge\lbrack S\sb2CS$(i-Pr)) $\sb2$, 6, and $\rm Me\sb2Ge\lbrack S\sb2CSEt\rbrack\sb2,$ 21, were determined. The immediate environment about germanium is that of distorted tetrahedron with monodentate ligands. The series of O-alkylmonothiocarbonate derivatives of triphenyl-, trimethyl- and diphenylgermanes have been prepared by reactions of $\rm R\sb3GeCl$ and $\rm Ph\sb2GeCl\sb2$ with $\rm NaSCO\sb2R\sp{\prime\prime}$, where R = Me and Ph, R$\sp{\prime\prime}$ = Me, i-Pr and n-Pr. The compounds were characterized by means of NMR, LR and Raman spectroscopy and X-ray crystallography. The crystal structures of $\rm Ph\sb3Ge\lbrack SCO\sb2Me\rbrack,$ 25, $\rm Ph\sb3Ge\lbrack SCO\sb2$(i-Pr)), 26, and $\rm Ph\sb2Ge\lbrack SCO\sb2Me\rbrack\sb2$, 28, were determined. In all cases the environment about germanium is essentially again that of a distorted tetrahedron with monodentate ligands. The triammonium salt, ($\rm NH\sb4\rbrack\sb3\lbrack S\sb2CSCH\sb2CH(NHCS\sb2)CO\sb2\rbrack,$ 34, was synthesized by the reaction of ammonia solution with L-cysteine and CS$\sb2$. The salt crystallizes as hexagonal in the $P6\sb5$ space group. Reaction of the salt with halotrimethylgermane produced the expected $\rm Me\sb3GeS\sb2CSCH\sb2CH(NHCS\sb2GeMe\sb3)CO\sb2GeMe\sb3,$ 35. This compound underwent CS$\sb2$ elimination, and further decomposed to give $\rm Me\sb3GeO\sb2$C(-CHNHC(S)SCH$\sb2$-), 37, which crystallizes as orthorhombic in the $P2\sb12\sb12\sb1$ space group. Diphenyl-/halodiphenyl- and dimethyi-/halodimethyltellurium monothiocarbonates of the form $\rm R\sp\prime\sb2Te\lbrack SCO\sb2R\rbrack$ or $\rm R\sp\prime\sb2TeX\lbrack SCO\sb2R\rbrack$ have been synthesized by reactions of $\rm R\sp\prime\sb2TeX\sb2$ with NaSCO$\sb2$R, where R$\sp\prime$ = Ph and Me, R = Me and i-Pr, X = Cl and $\sp{125}$I. The compounds were characterized by $\rm\sp1H,\ \sp{13}C$ and spectroscopy. The crystal structures of $\rm Me\sb2Te\lbrack SCO\sb2$(i-Pr)) $\sb2$, and $\rm Me\sb2TeCl\lbrack SCO\sb2Me\sb3$ were determined. The immediate environment about tellurium is that of the typical pseudo trigonal bipyramid. The dimethylbis(pyrrolidyl and piperidyl dithiocarbamato)tellurium(IV) compounds, $\rm Me\sb2Te\lbrack S\sb2CN(CH\sb2)\sb3CH\sb2\rbrack\sb2,$ and $\rm Me\sb2Te\lbrack S\sb2CN(CH\sb3)\sb4(CH\sb2)\rbrack\sb2,$ as well as the mixed-ligand derivative $\rm Me\sb2Te\{\lbrack S\sb2CN(CH\sb2)\sb3CH\sb2\rbrack \lbrack S\sb2CN(CH\sb2)\sb4(CH\sb2)\rbrack\}$ and the corresponding halodimethyl tellurium(IV) compounds, $\rm Me\sb2TeX\lbrack S\sb2CN(CH\sb2)\sb{n}CH\sb2\rbrack,$ where n = 3, 4, and X = Cl, Br, and I, have been prepared by reaction of $\rm Me\sb2TeX\sb2$ with the sodium salts of pyrrolidyl and piperidyl dithiocarbamaic acids. The compounds were characterized by elemental analysis, infrared, Raman, and $\rm\sp 1H,\ \sp{13}C$ and $\sp{125}$Te NMR spectroscopy, including some variable temperature NMR studies on the two bis compounds. The immediate environment about tellurium can be described as that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. (Abstract shortened by UMI.)Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1996 .Y35. Source: Dissertation Abstracts International, Volume: 59-08, Section: B, page: 4108. Adviser: John E. Drake. Thesis (Ph.D.)--University of Windsor (Canada), 1996.

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