The compounds [Cp*Zr(SR)(2)(mu(2)-SR)](2)(R=Bz (6), Et (7)) are prepared via reaction of Cp*ZrCl3 with 3 equiv of the respective sodium thiolate. The NMR data of 6 are consistent with a symmetric dimer in which two thiolate ligands bridge two Zr centers and the pentamethylcyclopentadienyl ligands adopt a cisoid geometry. In the case of 7, a mixture of three isomers of the dimeric complex is observed (cisoid (syn) 7a, transoid (anti) 7b, and transoid (syn) 7c). These species have been characterized by high-field NMR as well as crystallography in the case of 7b. Reaction of 6 with PMe(3) results in the monomeric adduct Cp*Zr(SBz)(3)(PMe(3)) (8). Reaction of 6 with MeOH yields the transoid dimer species [Cp*Zr(OMe)(2)(mu-OMe)](2) (9). The species [Cp*Zr(SBz)](2)(mu(2)-SBZ)(3)(mu(3)-O)Li(THF) (10) is also prepared and structurally characterized. Molecular mechanics and EHMO calculations of models based on the structures of 7b and 9 infer that the planarity at the bridging S or O atoms in these dimers arises as a result of steric factors rather than pi-bonding. This view is supported to some extent by the crystallographic study of 10. Compound 7b crystallizes in the space group P $($) over bar$$ 1, with a=9.580(3) Angstrom, b=12.210(2) Angstrom, c=9.222(3) Angstrom, alpha=95.01(2)degrees, beta=108.55(2)degrees, gamma=72.62(2)degrees, V=976.0(5) Angstrom(3), and Z=1. Compound 9 crystallizes in the space group P2(1)/n, with a=12.540(3) Angstrom, b=9.691 (3) Angstrom, c=13.165(3) Angstrom, beta =107.16(2)degrees, V=1529.3(7) Angstrom(3), and Z=2. Compound 10 crystallizes in the space group P $($) over bar$$ 1, with a=12.907(8) Angstrom, b=22.270(6) Angstrom, c=11.610(8) Angstrom, alpha=99.81(3)degrees, beta=114.59(6)degrees, gamma=79.24(3)degrees, V=2965(3) Angstrom(3), and Z=2.