The O-alkyl dithiocarbonate (xanthate) derivatives PhGe[S2CO(i-Pr)]3, Ph2Ge[S2CO(i-Pr)]2, Ph3Ge[S2CO(i-Pr)], Ph3Ge-[S2COMe], Ph3Ge[S2COEt], Ph3Ge[S2CO(n-Bu)], Ph2Ge[S2CO(n-Bu)]2, and possibly PhGe[S2COR]3, 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. The compounds were characterized by elemental analysis and infrared. Raman and 1H and 13C NMR spectroscopy. The crystal structures of Ph2Ge[S2CO(i-Pr)]2 and Ph3Ge[S2COR], where R = Me and i-Pr, were determined. Ph2Ge[S2COi-Pr]2 (2), which crystallizes as orthorhombic in space group (P212121, No. 19), has the cell parameters a = 8.406 (4) ?, b = 14.648 (5) ?, c = 19.551 (6) ?, V = 2407 (2) ?3, Z = 4, R = 0.0490, and Rw = 0.0501. The environment about germanium is essentially that of a distorted tetrahedron with monodentate xanthate ligands resulting in a S Ge-S angle of 103.2 (1)° and a C-Ge-C angle of 115.6 (3)° Ph3Ge[S2CO(iPr)] (3), which crystallizes as triclinic in space group (P1, No. 2), has the cell parameters, a = 11.039 (2) ?, b = 11.369 (2) ?, c = 9.299 (2) ?, α = 99.0 (1)°, β = 108.7 (2)°, γ = 99.1 (2)°, V = 1064 (1), Z = 2, R = 0.0576, Rw = 0.0584, and Ph3Ge[S2COMe] (4), which crystallizes as monoclinic in space group (Cc, No. 9), has the cell parameters a = 16.977 (9) ?, b = 8.510 (1) ?, c = 15.344 (5) ? β = 118.82 (2)°, V = 1942 (2) ?3, Z = 4, R = 0.0666, Rw = 0.0658 In both of the Ph3Gel. species, the environment about germanium is again essentially that of a distorted tetrahedron with monodentate ligands resulting in S-Ge-C angles ranging from 98.1 (2) to 112.2 (2)° for 3 and from 98.7 (4) to 114.6° for 4. The Ge-S bonding distances are 2.251 (3) and 2.252 (3) ? for 2, 2.270 (2) ? for 3, and 2.249 ? for 4. The Ge-O distances in 2 of 3.009 (8) and 2.981 (8) ? are similar to those found for 3, 3.146 (4) ?, and 4, 2.98 (1) ?.