Date of Award

1991

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

Keywords

Chemistry, Physical.

Rights

CC BY-NC-ND 4.0

Abstract

The O-alkyldithiocarbonate (xanthate) derivatives, PhGe (S$\sb2$COi-Pr) $\sb3$, Ph$\sb2$Ge (S$\sb2$COi-Pr) $\sb2$, Ph$\sb3$Ge (S$\sb2$COi-Pr), Ph$\sb3$Ge (S$\sb2$COMe), Ph$\sb3$Ge (S$\sb2$COEt), Ph$\sb3$Ge (S$\sb2$COn-Bu), Ph$\sb2$Ge (S$\sb2$COn-Bu) $\sb2$ and PhGe (S$\sb2$COR) $\sb3$, where R = Me, and Et, have been prepared in 60-86% yields by reaction of the sodium or potassium salt of the dithiocarbonic (xanthic) acid with trichlorophenyl-, dichlorodiphenyl- or chlorotriphenylgermane. Ph$\sb2$Ge(S$\sb2$COi-Pr) $\sb2$, 2, which crystallizes as orthorhombic in space group (P2$\sb1$2$\sb1$2$\sb1$, No. 19) has the cell parameters a = 8.406(4) A, b = 14.648(5) A, c = 19.551(6) A, V = 2407(2) A$\sp3$, Z = 4, R = 0.0490, and R$\sb{\rm w}$ = 0.0501. Ph$\sb3$Ge (S$\sb2$COi-Pr), 3, which crystallizes as triclinic in space group (P1, No. 2) has the cell parameters, a = 11.039(2) A, b = 11.369(2) A, c = 9.299(2) A, $\alpha$ = 99.0(1)$\sp\circ$, $\beta$ = 108.7(2)$\sp\circ$, $\gamma$ = 99.1(2)$\sp\circ$, V = 1064(1) A$\sp3$, Z = 2, R = 0.0576, Rw = 0.0584 and Ph$\sb3$Ge (S$\sb2$COMe), 4, which crystallizes as monoclinic in space group (Cc, No. 9) has the cell parameters a = 16.977(9) A, b = 8.510(1) A, c = 15.344(5) A, $\beta$ = 118.82(2)$\sp\circ$, V = 1942(2) A$\sp3$, Z = 4, R = 0.0666, R$\sb{\rm w}$ = 0.0658. Ph$\sb3$Ge (S$\sb2$COEt) crystallizes as triclinic in space group P1 (No. 2) with three molecules per asymmetric unit has the cell parameters a = 10.968(3) A, $\alpha$ = 90.80(2)$\sp\circ$, $\beta$ = 108.19(2), $\gamma$ = 108.23(2)$\sp\circ$, V = 3128(1) A$\sp3$, Z = 2, R = 0.0599, R$\sb{\rm w}$ = 0.0569. Three germanium tetrakis derivatives have been prepared by reacting GeCl$\sb4$ with an excess of potassium salts of methy, ethyl and isopropyl dithiocarbonates. The compounds were characterized by $\sp1$H and $\sp{13}$C NMR spectroscopy as well as infrared and Raman spectroscopy. The crystal structures of Ge (S$\sb2$COMe) $\sb4$, 1, and Ge (S$\sb2$COi-Pr) $\sb4$, 3, show geometry of a distorted tetrahedron. The xanthate groups in both the compounds show monodentate mode of linkage. Alkylgermanium dithiocarbonates are obtained by the reaction between potassium salts of methyl, ethyl and isopropyl dithiocarbonates with MeGeCl$\sb3$, t-BuGeCl$\sb3$ and n-Bu$\sb3$GeCl. All seven compounds MeGe (S$\sb2$COR) $\sb3$ where R = Me, Et and i-Pr, t-BuGe (S$\sb2$COR) $\sb3$ where R = Et and i-Pr, and n-Bu$\sb3$Ge (S$\sb2$COR) where R = Et and i-Pr, have been characterized by $\sp1$H and $\sp{13}$C NMR spectroscopy and infrared and Raman spectroscopy. The crystal structure of MeGe (S$\sb2$COEt) $\sb3$ has been determined. (Abstract shortened by UMI.)Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1992 .M585. Source: Dissertation Abstracts International, Volume: 53-12, Section: B, page: 6322. Thesis (Ph.D.)--University of Windsor (Canada), 1991.

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