CATALYTIC ACTIVITY OF SOME FLUOROTHIOLATE DERIVATIVES OF RHODIUM(I) - CRYSTAL-STRUCTURE OF [RH(MU-SC6H4F)(CO)2]2

The thiolato-bridged dinuclear compounds [Rh(μ-L)(CO)2]2, L = SC6F5 (1), p-SC6HF4 (2) and p-SC6H4F (3) have been obtained from the corresponding chloride-bridged species by reactions with the lead thiolates Pb(L)2. Compound 3 crystallizes in the space group P21/a with a = 17.2722(6), b = 8.9804(2), c = 25.1874(12) Å, β = 102.741(3)°, Z = 8. The values of the dihedral angles, 115.3(1) and 114.3(1)°, between the two coordination planes SRhS, for both molecules point to a "bent" geometry with intermetallic RhRh distances of 3.076(2) and 3.070(2) Å, which are consistent with assumed absence of metalmetal bonding. The [Rh(μ-L)(CO)2]2/nPPh3 systems involving 1 to 3 or the corresponding complex with L = SCF3 (4) have been studied as catalyst precursors for the hydroformylation of 1-hexene in dichloroethane at 5 bar and 30°C. The extent of aldehyde conversion ranges from 5 to 94%, with selectivities towards linear relative to branched aldehydes in the range 3 to 3.5. © 1990.