Stepwise construction of an iron-substituted rigid-rod molecular wire: targeting a tetraferra-tetracosa-decayne

Journal
Journal of the American Chemical Society  
Volume
135
Issue
10
Start Page
4051
End Page
4060
Citation
Journal of the American Chemical Society 135 (10): 4051-4060 (2013-03-13)
Publisher DOI
10.1021/ja400078c
Scopus ID
2-s2.0-84874962565
PubMed ID
23406332
Publisher
ACS Publications
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-C 4-Fe(depe)2-C4SiMe3 (3). Further modification of the termini gives the deprotected and stannylated compounds RC4-Fe(depe)2-C4-Fe(depe)2-C 4R (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 K c 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.
DDC Class
540: Chemie