1-[4- { 1,1′,1″,1‴-(1,3-Cyclopentadien-1,2,3,4-tetrayl)tetrakis} ]-(4,1-phenylen)-alkanone und deren Natrium-, Thallium(I)- und Fe(II)-Komplexe / 1-[4- { 1,1′,1″,1‴-(1,3-Cyclopentadiene-1,2,3,4-tetrayl)tetrakis} ](4,1 -phenylene)-alkanones and their Sodium, Thallium(I) and Iron(II) Complexes

Abstract

Tetraphenylcyclopentadiene (1) reacts with acylchlorides RC(O)Cl (R = CH3, C3H7, C5H11,C7H15) to form the corresponding [(cyclopentadiene tetrayl)tetrakis] (4,1-phenylene)alkanones C5H2(C6H4C(O)R-4)4 (2a, 2b, 2c and 2d). 2a reacts with NaNH2 generating the corresponding sodium salt Na[C5H(C6H4C(O)R-4)4] (3a). 2a, 2b, 2c, and 2d react with T1OC2H5 yielding the thallium(I) derivatives Tl[C5H(C6H4C(O)R-4)4] (4a, 4b, 4c, 4d). Octaphenylferrocene (5) reacts with acylchlorides RC(O)Cl (R = CH3, C3H7, C5H11, C7H15) to form octaacylated ferrocenes Fe[C5H(C6H4C(O)R-4)4]2 (6a, 6b, 6c and 6d). 6a can also be prepared by reacting FeI2 with 3a. 6a reacts with NaOBr yielding Fe[C5H(C6H4C(O)OH-4)4]2 (7), which after reaction with C5H11OH and C7H15OH gives the corresponding octaesters Fe[C5H(C6H4C(O)OR-4)4]2 (8c and 8d). 6a and 6b are reduced by N2H4(H2O) to give Fe[C5H(C6H4CH2R-4)4]2 (11a and 11b). The X-ray crystal structures of tetraphenylcyclopentadiene (2 a), as well as of the partially and totally substituted ferrocene derivatives Fe[C5H(C6H4C(O)CH3-4)4][C5H(C6H4C(O)CH3-4)3(C6H5)] (9), Fe[C5H(C6H4C(O)C3H7-4)(C6H5)3]2 (10) and Fe[C5H(C6H4C4H9-4)4]2 (11b) have been determined. The 1H and 13C NMR spectra of the new compounds are reported and discussed.