Attempts to isolate organogermanium derivatives at three different sites in a ligand prepared from cysteine are reported. The formation of Me3GeS2CSCH2CH(NHCS2GeMe3)CO2GeMe3 is established by NMR spectroscopy. This derivative undergoes CS2 elimination followed by further decomposition and rearrangement to yield Me3GeO2C(-CHNHC(S)SCH2-). The crystal structures of Me3GeO2C(-CHNHC(S)SCH2-) and the starting salt, [NH4](3)[S2CSCH2CH(NHCS2)CO2] were determined. [NH4](3)[S2CSCH2CH(NHCS2)CO2] (1) crystallizes in the hexagonal space group (P6(5), No. 170) with the cell parameters a 10.305(4) Angstrom, b = 10.305(4) Angstrom, c = 23.740(5) Angstrom, V = 2183(1) Angstrom(3), Z = 6, R = 0.0553, R, 0.0438. Me3GeO2C(-CHNHC(S)SCH2-) (4) crystallizes in the orthorhombic space group (P2(1)2(1)2(1), No. 19) with the cell parameters a 10.463(6) Angstrom, b = 22.644(5) Angstrom, c 10.241(5) Angstrom, V = 2426(1) Angstrom(3), Z = 4, R = 0.0571, R-w = 0.0472. The immediate environment about Ge is that of tetrahedral with the orientation of the terminal C=O bond being toward germanium. The Ge- - -O distance of 3.02(1) Angstrom is clearly less that the sum of the van der Waals radii of germanium and oxygen raising the possibility of a weak interaction. A plausible mechanism for the conversion of Me3GeCSCH2CH(NHCS2GeMe3)CO2GeMe3 into Me3GeO2C(-CHNHC(S)SCH2-) is proposed.