When the cyclic thioethers L = and were added to [(η5-C5H5)2Rh2(μ-CO)(μ-η2:η2-CF3C2CF3)] (1), the coordinative addition products [(η5-C5H5)2Rh2(CO)(μ-η1:η1-CF3C2CF3)L] (2a−c) were formed reversibly. When it is left in solution in the presence of excess ligand, the propylene sulfide complex 2b (L = transforms to the bridging sulfido complex [(η5-C5H5)2Rh2{μ-η1:η1:η2-C(O)C(CF3)C(CF3)}(μ-S)] (3a). A similar reaction occurred, but to a lesser extent, with the trimethylene sulfide complex 2a (L = Comparable decompositions do not occur with the tetrahydrothiophene complex 2a (L = The dimethylselenane complex [(η5-C5H5)2Rh2(CO)(μ-η1:η1-CF3C2CF3)(SeMe2)] (4a) was formed reversibly when SeMe2 was added to solutions of 1. The reactions of 1 with the organotelluranes L‘ = TeMe2 and TeEt2 gave solid addition products [(η5-C5H5)2Rh2(CO)(μ-η1:η1-CF3C2CF3)L‘] (4b,c), which remained intact when dissolved in polar solvents. No rearrangement products were formed when solutions of the tellurane addition products were kept for several days. The bridging sulfido complex 3a and the analogous complexes [(η5-C5H5)2Rh2{μ-η1:η1:η2-C(O)C(CF3)C(CF3)}(μ-E)] (3b, E = Se; 3c, E = Te) were obtained from the direct reaction between E and the complex 1. Addition of the cyclic tellurane to 1 gave (6), which underwent rapid intramolecular ligand scrambling in solution. The crystal and molecular structure of 6 was determined by X-ray crystallography.

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The coordinative addition of dimethyl sulfide to (C5H5)2Rh2(p-CO)(p-CF3C2CF3) is followed by an intramolecular transformation to give (C5H5)2Rh2(p-SCH2Me){ p-C(CF3)CH(CF3)}, and the corresponding reaction with Et2S gives a related complex with a chiral bridging sulfido group SCHMeEt.

The reaction of the binuclear rhodium complex [(ηϪC 5 H 5 ) 2 Rh 2 (μ-CO)(μ-η 1 :η 1 -C 2 (CF 3 ) 2 )] with a series of dichalcogenides, R 2 E 2 (E ϭ S, Se, Te; R ϭ Me, Et, i-Pr, Ph, Fc; not all combinations) has provided mixtures of complexes, the majority of which have been characterized by standard spectroscopic techniques. These complexes arise as a consequence of carbonyl substitution followed by chalcogen-chalcogen bond cleavage giving [(675 (E ϭ Se, Te; R ϭ Me, Et, i-Pr, Ph, Fc; not all combinations). In the case of Te 2 R 2 the dichalcogenide products have been structurally characterized for the carbonyl insertion product (for R ϭ Et) and the simple cleavage case (for R ϭ i-Pr). In both, the putative msymmetry is broken by substituent dispositions and, in the R ϭ Et adduct, torsion in the fluorocarbon skeleton.

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