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

Abstract

The novel three-µ-CO-containing trianions {[(µ-CO)Fe 2 (CO) 6 ] 3 [(µ-SCH 2 CH 2 ) 3 N]} 3-(4A) and {[(µ-CO)Fe 2 (CO) 6 ] 3 [1,3,5-(µ-SCH 2 ) 3 C 6 H 3 ]} 3-(4B) were prepared by reaction of 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 in 1:3:3 molar ratio in THF at room temperature. Further in situ treatment of 4A with electrophiles Ph 2 PCl, PhSBr, PhC(Cl)dNPh, and CH 2 dCHCH 2 Br afforded starlike complexes [(µ-Y)Fe 2 (CO) 6 ] 3 -[(µ-SCH 2 CH 2 ) 3 N] (5-8: Y ) Ph 2 P, PhS, PhCdNPh, CH 2 dCHCH 2 ), whereas its reaction with CS 2 followed by treatment with organic halides RX produced complexes [(µ-Y)Fe 2 (CO) 6 ] 3 -[(µ-SCH 2 CH 2 ) 3 N] (9-11: Y ) MeSCdS, PhCH 2 SCdS, CH 2 dCHCH 2 SCdS). Similarly, 4B reacted in situ with Ph 2 PCl, PhSBr, PhC(Cl)dNPh, CH 2 dCHCH 2 Br, and PhNCS to give starlike complexes [(µ-Y)Fe 2 (CO) 6 ] 3 [1,3,5-(µ-SCH 2 ) 3 C 6 H 3 ] (12-16: Y ) Ph 2 P, PhS, PhCdNPh, CH 2 dCHCH 2 , PhNHCdS), whereas its reaction with CS 2 followed by treatment with RX yielded complexes [(µ-Y)Fe 2 (CO) 6 ] 3 [1,3,5-(µ-SCH 2 ) 3 C 6 H 3 ] (17-19: Y ) MeSCdS, PhCH 2 SCdS, CH 2 dCHCH 2 SCdS). 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.

Recent studies on chemistry of novel μ-CO-containing butterfly Fe/E (E = S, Se, Te) cluster salts

“…The in situ reaction of cluster salt D⋅[Et 3 NH] 3 with electrophiles that contain a leaving group such as Ph 2 PCl is found to give the pyramidal N atom-centralized, three butterfly 2FeSP cluster cores-containing starlike cluster complex 13 (Scheme 12). The 31 P NMR spectrum of 13 shows one singlet at 142 ppm, which means that the three μ-P atoms in 13 have basically the same chemical environment [27,28] .…”

“…When this cluster salt is treated with electrophiles without a leaving group such as CS 2 , another cluster salt m 13 is first formed, and then further treatment of m 13 with alkyl halides results in formation of the planar benzene ringcentralized starlike Fe/S cluster complexes 14 (Scheme 13) [27,28] . Figure 9 shows the crystal structure of complex 14 (R = Me).…”

“…Figure 9 shows the crystal structure of complex 14 (R = Me). As shown in Figure 9, complex 14 is composed of three butterfly 2Fe2SC subcluster cores, which are connected to the α-C atoms of the centralized benzene ring via the equatorial S1-C25, S2-C26 and S3-C27 bonds to form the starlike molecule [19,20,28] .…”

Synthesis, characterisation of two hexa-iron clusters with {Fe2S2(CO)x} (x=5 or 6) fragments and investigation into their inter-conversion

“…Reactions of thiols and iron-carbonyl precursors afford a large collection of iron-sulfur-carbonyl complexes, which often possess novel structures and exhibit unusual chemical reactivity [16][17][18][19]. Trithiol ligand, 2-(mercaptomethyl)-2-methylpropane-1,3-dithiol, H 3 L, first described by Bosnich and coworkers [20] is a universal ligand reacting with a variety of transition metals [21][22][23].…”

新颖蝶状Fe/E/μ-CO (E = S, Se, Te)簇盐的化学研究进展

“…由图可见, 它 含有 3 个蝶状 2FeSP 子簇, 这三个子簇通过它们的 S1, S2 和 S3 以平伏键与处于中央部位的三乙撑胺 基的β-C 原子相连而构成星状分子 [19,20,27] . [27,28] . [19,20,28] .…”