Summary
The thiolato-bridged dinuclear compounds [Rh(μ-SR)-(COD)]2, where R=p-C6HF4 (1),p-C6H4F (2) and CF3 (3), are obtained from the chloro-bridged analogue by ligand exchange.
Compound (1) crystallizes in the space group P1 with a=9.740(3)Å, b=11.642(4)Å, c=13.997(6)Å, α=103.87(3)°, β=106.98(3)° and γ=105.10(2)°; z=2. In this dinuclear molecule both Rh atoms have a square planar coordination sharing one edge, namely the two sulphur bridging atoms. The Rh—Rh separation of 2.96 Å is consistent with at most a very weak metal-metal interaction. Upon addition of CO the dimeric [Rh(μ-SR)(CO)2]2 (4), (5) and (6) are obtained, but addition of PPh3 affords the monomeric species [Rh(SR)(PPh3)-(COD)] (7), (8) and (9). Reactions of the dimeric tetracarbonyl derivatives with PPh3 vary with the nature of R; [Rh(μ-SR)(PPh3)(CO)]2 is obtained when R=p-C6H4F (10) and CF3 (11) but monomeric [Rh(SR)-(PPh3)(CO)2] (12) is produced when R=p-C6HF4. The latter mononuclear compounds, with R=p-C6H4F (13) and CF3 (14), are also formed by reaction of [Rh(SR)-(PPh3)(COD)] with CO.
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Cruz-Garritz, D., Garcia-Alejandre, J., Torrens, H. et al. Polyfluorothiolate derivatives of rhodium(I). Crystal and molecular structure of [Rh(μ-SC6HF4)(C8H12)]2 . Transition Met Chem 16, 130–135 (1991). https://doi.org/10.1007/BF01127888
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DOI: https://doi.org/10.1007/BF01127888