Date of Award
Chemistry and Biochemistry
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Thirty-three germanium derivatives of dithiocarbamic acid and dithiophosphoric acid of the general formula R(,n)GeX(,4-n-m)L(,m), where R = CH(,3), C(,4)H(,5), X = Cl, Br, I and L = SC(S)N(CH(,3))(,2), SC(S)N(C(,2)H(,5))(,2), SP(S)(OCH(,3))(,2), SP(S)(OC(,2)H(,5))(,2), with n = 0 - 4, m = 1 - 3, were synthesized in modest to high yields by reacting salts of the acids with the appropriate germanes. The intermediate dithiocarbamate halides were prepared by exchange reactions with trimethylsilyl bromide and iodide. The compounds were characterized by elemental analysis, vibrational and nuclear magnetic resonance spectroscopy, mass spectrometry and by single crystal X-ray structure determinations. In the ('1)H and ('13)C ('1)H nmr spectra, the chemical shifts of the Ge-CH(,3) groups shifted as if the dithiophosphates were equivalent to a chlorine atom, and the dithiocarbamates were equivalent to a bromine atom. In crystal structure of (CH(,3))(,2)Ge SC(S)N(CH(,3))(,2) Cl, the germanium atom is located in the center of a trigonal bipyramid. The molecule contains one long and one short Ge-S distance, a short C-N bond and a very long Ge-Cl bond. The short C-N distance, attributed to its partial double bond character, is consistent with the appearance of the (nu)(C-N) stretch in the infrared spectra around 1500 cm('-1 ). The long Ge-Cl distance accounts for a change in the position of the (nu)(Ge-Cl) band by 100 cm('-1) towards the far infrared region. The molecule is assumed to be formed by a nucleophilic attack of the dithiocarbamate group along the C(,2) axis bisecting the Cl-Ge-Cl angle in (CH(,3))(,2)GeCl(,2). In the crystal structure of (CH(,3))(,2)Ge SC(S)N(CH(,3))(,2) (,2), the germanium atom is in the center of a much distorted octahedron. The structure of CH(,3)Ge SC(S)N(CH(,3))(,2) Cl(,2) could only be partially solved. The structure is similar to that of (CH(,3))(,2)Ge SC(S)N(CH(,3) (,2)Cl. In sharp contrast to anisobidentate dithiocarbamates, the dithiophosphates are completely monodentate, which is considered a rarity among related compounds. In the crystal structures of (C(,6)H(,5))(,3)Ge SP(S)(OCH(,3))(,2) , (C(,6)H(,5))(,2)Ge SP(S)(OCH(,3))(,2) (,2), and C(,6)H(,5)Ge SP(S)(OCH(,3))(,2) (,3), the germanium atom retains its tetrahedral geometry. Not only are the dithiophosphate groups monodentate, but the non-bonding sulfur atoms are turned as far away as possible from the germanium atom.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1986 .S275. Source: Dissertation Abstracts International, Volume: 47-05, Section: B, page: 1972. Thesis (Ph.D.)--University of Windsor (Canada), 1986.
SARKAR, ANIL B., "PREPARATION, CHARACTERIZATION AND CRYSTAL STRUCTURES OF ORGANOGERMANIUM DITHIOCARBAMATES AND DITHIOPHOSPHATES." (1986). Electronic Theses and Dissertations. 3176.