211302-12-4Relevant academic research and scientific papers
Synthesis, spectroscopic characterization, and structural studies of organogermanium tri- and monothiocarbonates. Crystal structures of Me2Ge[S2CSEt]2, Ph3Ge[SCO2Me], Ph3Ge[SCO2(i-Pr)], and Ph2Ge[SCO2Me]2
Drake, John E.,Yang, Jincai
, p. 319 - 334 (2007/10/03)
Two series of S-alkyl trithiocarbonate derivatives of dimethylgermane, Me2Ge[S2CSR]2, and halodiphenylgermane, Ph2GeX[S2CSR], where R = Me, i-Pr, n-Pr, n-Bu and X = Cl, Br, and three series of O-alkyl monothiocarbonate derivatives of triphenylgermane, Ph3Ge[SCO2R], diphenylgermane, Ph2Ge[SCO2R], and trimethylgermane, Me3Ge[SCO2R], where R = Me, i-Pr, and n-Pr, have been prepared in 73-92% yields by the reaction of the potassium or sodium salt of the appropriate tri- or monothiocarbonic acid with dichlorodimethyl-, chlorotriphenyl-, dichlorodiphenyl-, and chlorotrimethylgermane. The compounds were principally characterized by infrared, Raman, and 1H and 13C NMR spectroscopy, including some variable temperature studies, as well as by mass spectrometry. Me2Ge[S2CSEt]2, 1: P21/m (No. 11) with cell parameters a = 6.647(4) A, b = 7.423(2) A, c = 16.290(4) A, β = 91.07(3)°, V = 803.6(4) A3, Z = 2, R = 0.0484, Rw = 0.0485. Ph3Ge[SCO2Me], 13: P1 (No. 2) with cell parameters a = 9.970(4) A, b = 10.660(3) A, c = 9.853(2) A, α = 101.78(2)°, β = 109.98(2)°, γ = 89.76(3)°, V = 961.0(5) A3, Z = 2, R = 0.0534, Rw = 0.0451. Ph3Ge[SCO2(i-Pr)], 14: P1 (No. 2) with cell parameters a = 14.386(7) A, b = 18.598(6) A, c = 9.223(3) A, α = 102.85(3)°, β = 94.58(3)°, γ = 108.13(3)°, V = 2256(1) A3, Z = 2, R = 0.0545, Rw = 0.0552. Ph2Ge[SCO2Me]2, 16: Cc, (No. 9) with cell parameters a = 11.790(4) A, b = 13.696(5) A, c = 23.232(6) A, β = 92.26(3)°, V = 3748(2) A3, Z = 8, R = 0.0563, Rw = 0.0512. The immediate environment about Ge is that of tetrahedral but the orientations of the thiocarbonate groups display interesting features.
Synthesis and spectroscopic characterization of S-ethyl, S-isopropyl, S-n-propyl, and S-n-butyl trithiocarbonate (trixanthate) derivatives of trimethyl- and triphenylgermane and diphenyldigermane. Crystal structure of Ph2Ge[S2CS(i-Pr)]2
Drake, John E.,Yang, Jincai
, p. 854 - 860 (2008/10/08)
The S-alkyl trithiocarbonate (trixanthate) derivatives Me3Ge[S2CSR], Ph3Ge[S2CSR], and Ph2Ge[S2CSR]2, where R = Et, i-Pr, n-Pr, and n-Bu, have been prepared in 73-85% yields by the reaction of the potassium salt of the appropriate trithiocarbonic (trixanthic) acid with iodotrimethylgermane, bromotriphenylgermane, or dichlorodiphenylgermane. The compounds were characterized by infrared, Raman, and 1H and 13C NMR spectroscopy. The crystal structure of Ph2Ge[S2CS(i-Pr)]2 was determined, and it crystallizes in space group P1 (No. 2) with the cell parameters a = 10.752(9) ?, b = 13.36(1) ?, c = 9.64(2) ?, α = 105.8(1)°, β = 113.2(1)°, γ = 91.79(9)°, V = 1211(3) ?3, and Z = 2; R = 0.0638, and Rw = 0.0626. The environment about germanium is essentially that of a distorted tetrahedron with monodentate linkages resulting in S-Ge-S and C-Ge-C angles of 87.3(2) and 118.1-(3)°, respectively, and S-Ge-C angles ranging from 110.3(3) to 113.4(3)°. The Ge-S bond distances are 2.278(5) and 2.284(5) ?, and the Ge-C bond distances are 1.925(7) and 1.941(9) ?. The terminal (C=S) sulfur atoms are oriented toward the germanium center at distances of 3.224(5) and 3.304(5) ?. All of these trixanthate derivatives are unstable as a result of the ready elimination of carbon disulfide.
