1396688-30-4Relevant articles and documents
Formation, spectroscopic characterization, and solution stability of an [Fe4S4]2+ cluster derived from β-cyclodextrin dithiolate
Lo, Wayne,Zhang, Ping,Ling, Chang-Chun,Huang, Shaw,Holm
, p. 9883 - 9892 (2012/11/13)
The formation and solution properties, including stability in mixed aqueous-Me2SO media, have been investigated for an [Fe 4S4]2+ cluster derived from β-cyclodextrin (CD) dithiolate. Clusters of the type [Fe4S4(SAr) 4]2- (Ar = Ph, C6H4-3-F) are generated in Me2SO by redox reactions of [Fe4S 4(SEt)4]2- with 2 equiv of ArSSAr. An analogous reaction with the intramolecular disulfide of 6A,6 D-(3-NHCOC6H4-1-SH)2-6 A,6D-dideoxy-β-cyclodextrin (14), whose synthesis is described, affords a completely substituted cluster formulated as [Fe 4S4{β-CD-(1,3-NHCOC6H4S) 2}2]2- (15). Ligand binding is indicated by a circular dichroism spectrum and also by UV-visible and isotropically shifted 1H NMR spectra and redox behavior convincingly similar to [Fe 4S4(SPh)4]2-. One formulation of 15 is a single cluster to which two dithiolates are bound, each in bidentate coordination. With there being no proven precedent for this binding mode, we show that the cluster [Fe4S4(S2-m-xyl) 2]2- is a single cubane whose m-xylyldithiolate ligands are bound in a bidentate arrangement. This same structure type was proposed for a cluster formulated as [Fe4S4{β-CD-(1,3-SC 6H4S)2}2]2- (16; Kuroda et al. J. Am. Chem. Soc.1988, 110, 4049-4050) and reported to be water-stable. Clusters 15 and 16 are derived from similar ligands differing only in the spacer group between the thiolate binding site and the CD platform. In our search for clusters stable in aqueous or organic-aqueous mixed solvents that are potential candidates for the reconstitution of scaffold proteins implicated in cluster biogenesis, 15 is the most stable cluster that we have thus far encountered under anaerobic conditions in the absence of added ligand.
