Kristallstrukturen ferrocenhaltiger 1,3-Diketon- und Enaminoketon-Derivate

Abstract

Professor Kurt Dehnicke zum 70. Geburtstag gewidmet Inhaltsu È bersicht. Es wurden die Kristallstrukturen der 1,3-Diketone 2,4-Dioxo-4-ferrocenyl-butansa È ureethylester (1) und Ferrocen-1,1'-bis(2,4-dioxobutansa È ureethylester) (2) bestimmt. Durch Umsetzung von 1 mit Cu(ac) 2´H2 O in THF wurde der Kupfer(II)-Komplex Aqua-bis(3-ethoxycarbonyl-1-ferrocenyl-propan-1,3-dionato)-kupfer(II) (1 a) erhalten, der ebenfalls strukturell charakterisiert werden konnte. Des-weiteren wurden die Strukturen der Enaminoketone 2,2'-(1,4-Phenylendiamino)-bis(4-ferrocenyl-4-oxo-but-2-ensa È ureethylester) (3) und Ferrocen-1,1'-bis(4-oxo-2-phenylaminobut-2-ensa È ureethylester) (4) ro È ntgenographisch bestimmt. Erga È nzt wurden die strukturanalytischen Daten durch elektrochemische Untersuchungen.Abstract. The crystal structures of the 1,3-diketones 2,4-dioxo-4-ferrocenyl-butanoic acid ethylester (1) und ferrocene-1,1'-bis(2,4-dioxo-butanoic acid ethylester) (2) have been determined. Through conversion of 1 by Cu(ac) 2´H2 O in THF the copper(II) complex aqua-bis(3-ethoxycarbonyl-1-ferrocenyl-propane-1,3-dionato) copper(II) (1 a) has been obtained, which is structurally characterized too. The structures of the enaminoketones 2,2'-(1,4-phenylenediamino)-bis(4-ferroce-nyl-4-oxo-but-2-enoic acid ethylester) (3) and ferrocene-1,1'bis(4-oxo-2-phenylamino-but-2-enoic acid ethylester) (4) have been determined by X-ray analysis as well. Electrochemical studies completed the structural investigations.

Ethyl (Z)-4-ferrocenyl-2-(4-hydroxyanilino)-4-oxobutenoate

“…As noted in the compounds previously reported, the O═ C-C═C-N moiety is planar and the bond lengths indicate electron delocalization (Shi et al, 2004). The O═C-C═C-N plane is twisted with respect to the benzene and substituted cyclopentadienyl rings by 44.2 (2) and 13.8 (3)° whereas the values in an analogous compound are 38.2 (2) and 2.5 (2)° (Prokop et al, 2001). Furthermore, the O═C-C═C-N plane and the O═ C-O plane make a dihedral angle of 55.5 (6)° which is greater than that (48.1 (4)°) of the analogous compound.…”

“…For background to the use of enaminones and enamine esters in coordination chemistry, supramolecular chemistry and organometallic chemistry, see: Prokop et al (2001); Elassar & El-Khair (2003); Kascheres (2003); Shi et al (2004Shi et al ( , 2006Shi et al ( , 2008. For related structures, see: Prokop et al (2001).…”

Bis(1-ferrocenylbutane-1,3-dionato-κ2O,O′)copper(II) and bis(1,3-diferrocenylpropane-1,3-dionato-κ2O,O′)copper(II)

“…The two ferrocene groups are anti in the complex, with the C5±C9 cyclopentadienyl ring rotated by 26.7 (1) with respect to the O1/C2±C4/O2 ligand plane. This arrangement differs from that of complex (III), in which the ferrocenyl groups are syn (Prokop et al, 1999), whilst in the aqua complex of (III), they are anti (Prokop et al, 2001). The cyclopentadienyl rings are in an eclipsed arrangement within each ferrocene group, with pseudo-torsion angles CÁ Á ÁCg1Á Á ÁCg2Á Á ÁC ranging from 0.79 to 1.39 (Cg1 and Cg2 are the centroids of the C5±C9 and C10± C14 cyclopentadienyl rings).…”

“…Compound (I) has been further characterized by elemental analysis and cyclic voltammetry (Zanello et al, 1998). Related complexes, namely bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dionato)copper(II), (III), and bis[1,3-bis(2-methylferrocenyl)propane-1,3-dionato]copper(II), have been prepared and characterized (Prokop et al, 1999(Prokop et al, , 2001Abiko & Wang, 1998).…”

Syntheses and Crystal Structures of Two Ferrocenyl Enamine Esters

“…Ethyl 2, 4-dioxo-4-ferrocenyl-butanoate, C 5 H 5 FeC 5 H 4 COCH 2 COCO 2 CH 2 CH 3 , was synthesized by a literature method [13][14][15]. Progress of reactions was monitored by TLC.…”