Binuclear Fulvalene and Bis(cyclopentadienyl)methane Halfsandwich Complexes of Manganese and Rhenium Containing Tetrahydrothiophene Ligands. X-Ray Structure Analysis of {(CO)2MnIC5H4- C 5H4lMn(CO)2}(/i-SC4H8)

The photo-induced substitution o f carbonyl ligands in the binuclear cyclopentadienyl-type complexes (CO)3M[C5H4(CH2)„C5H4]M(CO)3 (n = 0 (fulvalene), M = Mn (1) and Re (2); n = 1 (bis(cyclopentadienyl)methane), M = Mn (3) and Re (4)) has been studied in the presence o f tetrahydrothiophene, SC4H8 (tht). Photodecarbonylation o f 1 -4 in tetrahydrofuran solution leads to solvent-stabilized intermediates which react with tht in the dark to give monosubsti­ tuted derivatives (CO)3M[C5H4(CH 2)nC5H4]M(CO)2(tht) (la~4a). In the case o f M = Mn, thtbridged compounds {(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2}(Jw-tht) (n = 0 (lb) and n = 1 (3b)) are also obtained which are the exclusive products o f the photolysis o f 1 and 3 in benzene in the presence o f tht. Photodecarbonylation o f 1 4 in neat tetrahydrothiophene produces disubsti­ tuted derivatives in the case o f manganese, (tht)(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2(tht) (n = 0 (lc ) and n = 1 (3c)), whereas only the monosubstituted complexes 2a and 4a could be isolat­ ed in the case o f rhenium. The molecular structure o f the tht-bridged fulvalene complex lb has been determined by an X-ray structure analysis. A special reaction o f dimethyl disulfane with the photolyzed tetrahydrofuran solution o f 2 leads to the bis(methylthiolato) compound (CO)3Re[C5H4C 5H4]Re(CO)(SMe)2 (5). The new complexes were characterized by their IR spectra v(CO) and their 'H and 13C N M R spectra.