Reactions of the Three-μ-CO-Containing Trianions {[Fe2(μ-CO)(CO)6]3[(μ-SCH2CH2)3N]}3- and {[Fe2(μ-CO)(CO)6]3[1,3,5-(μ-SCH2)3C6H3]}3- To Give Starlike Complexes Terminated with Butterfly Fe/S Cluster Cores

Five starlike complexes with terminal butterfly Fe/S cluster cores, [Fe 2 (μ-Ph 2 P)(CO) 6 ] 3 [(μ-SCH 2 CH 2 ) 3 N] ( 2 ), [Fe 2 (μ-PhS)(CO) 6 ] 3 [(μ-SCH 2 CH 2 ) 3 N] ( 3 ), [Fe 2 (μ-PhC NPh)(CO) 6 )] 3 [1,3,5-(μ-SCH 2 ) 3 C 6 H 3 ] ( 5 ), and [Fe 2 (μ-RSC S)(CO) 6 ] 3 [1,3,5-(μ-SCH 2 ) 3 C 6 H 3 ] ( 7, R = Me; 8, R = PhCH 2 ), were prepared by a “one pot” reaction of the trithiol N(CH 2 CH 2 SH) 3 or 1,3,5-(HSCH 2 ) 3 C 6 H 3 with Fe 3 (CO) 12 and Et 3 N, followed by treatment of the intermediate three-μ-CO-containing trianions {[Fe 2 (μ-CO)(CO) 6 ] 3 [(μ-SCH 2 CH 2 ) 3 N]} 3 - ( 1 ) and {[Fe 2 (μ-CO)(CO) 6 ] 3 [1,3,5-(μ-SCH 2 ) 3 C 6 H 3 ]} 3 - ( 4 ) with Ph 2 PCl, PhSBr, PhC(Cl) NPh, CS 2 /MeI, and CS 2 /PhCH 2 Br, respectively. These products have been fully characterized by elemental analysis, spectroscopy, and X-ray crystallography.