title: Iron-Sulfur Clusters with SiMe(2)-Bridged Cyclopentadienyl Ligands: [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(5)S(12), [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6), and [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6)(CO).
abstract: The synthesis and characterization of iron-sulfur clusters stabilized by dimethylsilyl-bridged cyclopentadienyl groups are reported. The thermal reaction of Me(2)Si(eta(5)-C(5)H(4))(2)Fe(2)(CO)(4) (1) with S(8) yields the tetranuclear cubane-type cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6) (4) and the pentanuclear cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(5)S(12) (3) in high yields. The photochemical reaction of 1 with S(8) yields the tetranuclear cluster compound [Me(2)Si(eta(5)-C(5)H(4))(2)](2)Fe(4)S(6)(CO) (5), which contains one residual terminal carbonyl. The crystal structures of 3 and 4 have been determined. Crystal data: 3.CH(2)Cl(2), monoclinic, C2/c, a = 23.480(13) Å, b = 11.192 (4) Å, c = 17.84 (3) Å, beta = 118.58(9) degrees, V = 4118(7) Å(3), Z = 4, R = 0.078; 4, triclinic, P&onemacr;, a = 8.4787(7) Å, b = 12.9648(9) Å, c = 13.4990(9) Å, alpha = 79.857(8) degrees, beta = 75.293(8) degrees, gamma = 74.041(11) degrees, V = 1370.9(2) Å(3), Z = 2, R = 0.0447. The Fe(5)S(12) core of 3 has a bowtie structure in which a central iron atom is octahedrally coordinated by six sulfur atoms from one tetrasulfido and four disulfido groups. The structure of 4 resembles the structure of the known iron-sulfur cluster Cp(4)Fe(4)S(6). However, 4 shows a markedly enhanced thermal stability compared to Cp(4)Fe(4)S(6). In their cyclic voltammograms, 4 and 5 exhibit electrochemical behavior typical of cubane-type Cp-iron-sulfur clusters, whereas the cyclic voltammogram of 3 is quite different. The nu(CO) mode of 5 has been measured for four different oxidation states of the cluster by means of IR spectroelectrochemical methods. The Mössbauer spectra of 3 and 3(+) are in accordance with their pentanuclear structure.
authors.affiliation: Department of Inorganic Chemistry, Nijmegen SON Research Center, University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands, and Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany.
authors.forename: Wouter
authors.initials: W
authors.lastname: van Den Berg
authors.forename: Lianne
authors.initials: L
authors.lastname: Boot
authors.forename: Helma
authors.initials: H
authors.lastname: Joosen
authors.forename: Johannes G. M.
authors.initials: JG
authors.lastname: van Der Linden
authors.forename: Wil P.
authors.initials: WP
authors.lastname: Bosman
authors.forename: Jan M. M.
authors.initials: JM
authors.lastname: Smits
authors.forename: René
authors.initials: R
authors.lastname: de Gelder
authors.forename: Paul T.
authors.initials: PT
authors.lastname: Beurskens
authors.forename: Jürgen
authors.initials: J
authors.lastname: Heck
authors.forename: Anton W.
authors.initials: AW
authors.lastname: Gal