Synthesis and Characterization of Starlike Complexes Containing Three Terminal Butterfly Fe/S Cluster Cores Generated via Reactions of the Three-<i>μ</i>-CO-Containing Trianions {[(<i>μ</i>-CO)Fe₂(CO)₆]₃[(<i>μ</i>-SCH₂CH₂)₃N]}^3- and {[(<i>μ</i>-CO)Fe₂(CO)₆]₃[1,3,5-(<i>μ</i>-SCH₂)₃C₆H₃]}^3- with Electrophiles

The novel three-μ-CO-containing trianions {[(μ-CO)Fe2(CO)6]3[(μ-SCH2 CH2)3N]}3- (4A) and {[(μ-CO)Fe2(CO)6]3[1,3,5-(μ-SCH2)3C6H3]}3- (4B) were prepared by reaction of trithiol N(CH2CH2SH)3 or 1,3,5-(HSCH2)3C6H3 with Fe3(CO)12 and Et3N in 1:3:3 molar ratio in THF at room temperature. Further in situ treatment of 4A with electrophiles Ph2PCl, PhSBr, PhC(Cl)NPh, and CH2CHCH2Br afforded starlike complexes [(μ-Y)Fe2(CO)6]3[(μ-SCH2CH2)3N] (5−8: Y = Ph2P, PhS, PhCNPh, CH2CHCH2), whereas its reaction with CS2 followed by treatment with organic halides RX produced complexes [(μ-Y)Fe2(CO)6]3[(μ-SCH2CH2)3N] (9−11: Y = MeSCS, PhCH2SCS, CH2CHCH2SCS). Similarly, 4B reacted in situ with Ph2PCl, PhSBr, PhC(Cl)NPh, CH2CHCH2Br, and PhNCS to give starlike complexes [(μ-Y)Fe2(CO)6]3[1,3,5-(μ-SCH2)3C6H3] (12−16: Y = Ph2P, PhS, PhCNPh, CH2CHCH2, PhNHCS), whereas its reaction with CS2 followed by treatment with RX yielded complexes [(μ-Y)Fe2(CO)6]3[1,3,5-(μ-SCH2)3C6H3] (17−19: Y = MeSCS, PhCH2SCS, CH2CHCH2SCS). All the starlike complexes 5−19 contain three terminal butterfly Fe/S cluster cores, which have been fully characterized by elemental analysis and spectroscopy, and particularly by X-ray diffraction techniques for 5, 12, 15, and 17.