Characterization of the Self-Condensation Equilibrium of [Fe(4)S(4)(SH)(4)](2-): Spectroscopic Identification of a Unique Sulfido-Bridged Acyclic Tricubane Cluster.
Our interest in higher nuclearity sulfido-bridged Fe-S clusters, because of their occurrence in several proteins including nitrogenase, prompted us to investigate the solution chemistry of the functionalized cluster [Fe(4)S(4)(SH)(4)](2)(-) (1). (n-Pr(4)N)(2)[1] crystallizes in space group P2(1)/n of the monoclinic system with a = 26.201(1) Å, b = 11.4999(5) Å, c = 28.090(1) Å, and beta = 110.735(1) degrees. The X-ray structure reveals the conventional cubane-type geometry with an [Fe(4)S(4)](2+) core symmetry more closely approaching T(d)() than the tetragonally distorted D(2)(d)() symmetry reported for the (PPh(4))(2)[1] (Müller, A.; Schladerbeck, N. H.; Bögge, H. J. Chem. Soc., Chem. Commun. 1987, 35). In solution, 1 exists in dynamic equilibrium with self-condensation products formed through elimination of H(2)S and formation of sulfido-bridged cluster oligomers, one of which (4) is prevalent. The self-condensation equilibrium is shifted toward cluster 1. When acetonitrile solutions of 1 were treated with thiols more acidic than H(2)S, it was possible to detect hydrosulfido terminal ligand substitution products of 1 as well as those of the major self-condensation product 4. Detailed analysis of the products in acetonitrile solutions of 1, as well as those generated in solutions of 1 treated with acidic thiol, by electrospray mass spectrometry, and both (19)F and (1)H NMR spectroscopy indicates the presence of a sulfido-bridged acyclic trimer of [Fe(4)S(4)](2+) clusters, i.e. {[Fe(4)S(4)(SH)(3)](2)[Fe(4)S(4)(SH)(2)](&mgr;-S)(2)}(6)(-) (4), a hitherto unprecedented Fe-S structural pattern, as the principal Fe-S cluster self-condensation product.
Hoveyda
H. R.
HR
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138.
Holm
R. H.
RH