When solutions of [Cp 2Rh 2( μ-CO)( μ- η 2: η 2-CF 3C 2CF 3)] ( I) in petroleum ether or chlorinated hydrocarbons were treated with the dialkylsulfanes SRR′(R=R′=Me, Et, Pr, Bz; RR′=MeEt), the addition products [Cp 2Rh 2(CO)(SRR′)( μ- η 1: η 1-CF 3C 2CF 3)] ( III, a– e) were formed reversibly. The complexes ( III) have been characterized spectroscopically in solutions containing excess ligand. Removal of excess ligand and solvent regenerated ( I). When left in solution, a number of the dialkylsulfane complexes underwent interesting transformations. The complex ( IIIa, R=R′=Me) converted to [Cp 2Rh 2{ μ- η 1: η 2-C(CF 3)C(CF 3)H}( μ 2-SEt)] ( IVa, R=Et); this involves a β-proton transfer accompanied by a Stevens rearrangement to convert {S(CH 2 −)CH 3} to (SCH 2CH 3) −. The structure of ( IVa) was determined by X-ray crystallography. Two rearrangement products were formed when ( IIIb, R=R′=Et) was left in solution. One was characterized from spectroscopic data as [Cp 2Rh 2{ μ- η 1: η 2-C(CF 3)C(CF 3)H}( μ 2-SCHMeEt)] ( IVb), which is formed by a Stevens rearrangement after transfer of a β-proton. The other was identified as ( IVa, R=Et), which is formed after proton abstraction from a γ-carbon followed by elimination of ethene. A number of μ-thiolato complexes ( IV a– h, R=Me, Et, Pr, CHMeEt, Pr i , Bu, Bu t and Ph) were formed directly by treatment of ( I) with the appropriate alkanethiol RSH. In some instances (R=CHMeEt, Pr i , and Bu t ), a second product of formula [Cp 2Rh 2( μ-CO){ μ- η 2: η 1-CH(CF 3)C(CF 3)SCR 1R 2R 3)] ( VI, a– c) was formed. The molecular structure of ( VIb, R 1=H, R 2=R 3=Me) was determined by single crystal X-ray diffraction analysis.