A new class of diiron arene complexes with disulfide ...
|Title||A new class of diiron arene complexes with disulfide and diamine bridges.|
|Author(s)||A. Abd-El-Aziz, K. Epp, C. de Denus, G. Fisher-Smith|
|Journal||Section Title: Organometallic and Organometalloidal Compounds, Organometallics|
|Abstract||The synthesis and characterization of a new class of bis(cyclopentadienyliron) arene complexes of disulfides and diamines with aliph. and arom. bridges are presented. Reactions of the arom. or aliph. dithiols with a wide range of cyclopentadienyliron complexes of chloroarenes (1a-i; shown as I; X = Cl, R = H, 2-, 3- and 4-Me, 2-, 3-, and 4-Cl, 2,6-Me2, 2,5-Me2), in the presence of potassium carbonate in a 4:1 THF/DMF mixt., gave the dicationic iron species [shown as II; Q = Y = S, Z = 1,2-, 1,3-, and 1,4-phenylene, same R 3a-k; same Q, R, Z = (CH2)x, x = 2, 4, 6 7a-s] in high yields. The synthesis of diiron systems with ether/thioether linkages was also found to be successful. In these reactions, 4-hydroxythiophenol (4) was used as an example with various chloroarene complexes to give the bis(cyclopentadienyliron) arene dications with ether/thioether bridges II (Q = O, Y = S, Z = 1,4-phenylene 5a-f). Reactions of chloroarene complexes (1a, g) with 1,6-hexanediamine (8a) resulted in the formation of the diiron complexes II [Q = Y = NH, Z = (CH2)6, R = H, 4-Cl 9a, b] in very poor yields (28 and 17%, resp.). However, the use of nitroarene complexes I (X = NO2, R = H, 2-, 3-, and 4-Me, 2,6-Me2, 2,5-Me2 11a-f) as starting materials proved to increase the reaction yields and decreases the reaction time, which minimized product decompn. in the prepn. of complexes 9a and II [Q = Y = NH, Z = (CH2)x, x = 2, 4, 6, same R 12a-n]. The change in the no. of methylene groups of the aliph. diamines from 2 to 6 resulted in an increase in the product yield. Arom. diamine bridges were also introduced to yield complexes II (R = H, 3- and 4-Me, Q = Y = NH, Z = 1,3- and 1,4-phenylene 14a-e) in a similar fashion. The proposed synthetic strategy allowed for the synthesis of a larger no. of diiron complexes with various heteroatom linkages, while the traditional route to similar complexes (ligand-exchange reaction of ferrocene with the appropriate arom. compd.) proved to be unsuccessful in terms of yield and versatility. [on SciFinder(R)]|
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