Catalytic activity of some fluorothiolate derivatives of rhodium(I). Crystal structure of 2

Article abstract of DOI:10.1016/0022-328X(90)87013-4

The thiolato-bridged dinuclear compounds 2, L = SC6F5 (1), p-SC6HF4 (2) and p-SC6H4F (3) have been obtained from the coresponding 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) Angstroem, β = 102.741(3) deg, Z = 8.The values of the dihedral angles, 115.3(1) and 114.3(1) deg, between the two coordination planes S-Rh-S, for both molecules, point to a "bent" geometry with intermetallic Rh-Rh distances of 3.076(2) and 3.070(2) Angstroem, which are consistent with assumed absence of metal-metal bonding. The 2/nPPh3 system involving 1 to 3 or the corresponding complex with L = SCF3 (4) have been studied as catalyst precursor for the hydroformylation of 1-hexene in dichloromethane at 5 bar and 30 deg C.The extent of aldehyde conversion ranges from 5 to 94percent, with selectivities towards linear relative to branched aldehydes in the range 3 to 3.5.