Synthesis, spectroscopic characterization, and structural studies of organogermanium tri- and monothiocarbonates. Crystal structures of Me<sub>2</sub>Ge[S<sub>2</sub>CSEt]<sub>2</sub>, Ph<sub>3</sub>Ge[SCO<sub>2</sub>Me], Ph<sub>3</sub>Ge[SCO<sub>2</sub>(<i>i-</i>Pr)], and Ph<sub>2</sub>Ge[SCO<sub>2</sub>Me]<sub>2</sub>

Two series of S-alkyl trithiocarbonate derivatives of imethylgermane, 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) Å, b = 7.423(2) Å, c = 16.290(4) Å, β = 91.07(3)°, V = 803.6(4) Å3, Z = 2, R = 0.0484,Rw = 0.0485. Ph3Ge[SCO2Me],13: P1bar (No. 2) with cell parameters a = 9.970(4) Å, b = 10.660(3) Å, c = 9.853(2) Å, α = 101.78(2)°, β = 109.98(2)°, γ = 89.76(3)°, V = 961.0(5) Å3, Z = 2, R = 0.0534, Rw = 0.0451. Ph3Ge[SCO2(i-Pr)], 14: P 1bar (No. 2) with cell parameters a = 14.386(7) Å, b = 18.598(6) Å, c = 9.223(3) Å, α = 102.85(3)°, β = 94.58(3)°, γ = 108.13(3)°, V = 2256(1) Å3, Z = 2, R = 0.0545, Rw = 0.0552. Ph2Ge[SCO2Me]2, 16: Cc, (No. 9) with cell parameters a = 11.790(4) Å, b = 13.696(5) Å, c = 23.232(6) Å, β = 92.26(3)°, V = 3748(2) Å3, 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.Key words: structure, germanium, phenyl, methyl, thiocarbonates.