title: Stepwise construction of an iron-substituted rigid-rod molecular wire: targeting a tetraferra-tetracosa-decayne.
abstract: trans-Fe(depe)2I2 (depe =1,2-bis(diethylphosphino)ethane) was employed to stepwise incorporate Fe(II) centers into a rigid-rod butadiyne based 5,10,15,20-tetraferratetracosa-1,3,6,8,11,13,16,18,21,23-decayne. The iterative synthesis first connects two Fe(II) centers via a central butadiynediyl ligand to provide I-Fe(depe)2-C4-Fe(depe)2-I (2), then extends the system by substituting the terminal halides of 2 to yield Me3SiC4-Fe(depe)2-C4-Fe(depe)2-C4SiMe3 (3). Further modification of the termini gives the deprotected and stannylated compounds RC4-Fe(depe)2-C4-Fe(depe)2-C4R (4 and 5; R = H, Sn(CH3)3, respectively). Transmetalation with two more mononuclear units furnishes the homometallic tetranuclear compound I-Fe(depe)2-C4-Fe(depe)2-C4-Fe(depe)2-C4-Fe(depe)2-I (6), to which two more butadiynyl units were attached to give Me3SiC4-Fe(depe)2-C4-Fe(depe)2-C4-Fe(depe)2-C4-Fe(depe)2-C4SiMe3 (7). All compounds were characterized by NMR, IR, and Raman spectroscopies and by elemental analyses. X-ray diffraction studies were carried out on the dinuclear complexes revealing highly symmetrical rigid-rod structures. Cyclic voltammetric studies showed that compounds 2-7 undergo reversible and well-defined oxidations with high Kc values indicating thermodynamically stable mixed valence species. While the number of the oxidation waves of compounds 2, 6, and 7 are equivalent to the number of metal centers, the dinuclear complexes 3, 4, and 5 exhibit three reversible oxidation waves, one at significantly more positive potential. Two redox waves were attributed to the oxidation of the metal centers, while the remaining one is due to the oxidation of the butadiynediyl ligand. The electronic properties of complexes 2, 3, and 7 were investigated by spectroelectrochemical measurements.
authors: Institute of Inorganic Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
authors: Franziska
authors: F
authors: Lissel
authors: Thomas
authors: T
authors: Fox
authors: Olivier
authors: O
authors: Blacque
authors: Walther
authors: W
authors: Polit
authors: Rainer F
authors: RF
authors: Winter
authors: Koushik
authors: K
authors: Venkatesan
authors: Heinz
authors: H
authors: Berke
mesh_terms: D055664:Electrochemical Techniques; D005296:Ferrous Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure
chemical_list: D005296:Ferrous Compounds