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Synthesis and Reactivity of Ferrocenyl Substituted Bis(amino)gallanes

Feier-Iova, Ovidiu Cristian

German Title: Synthese und Reaktivität von Ferrocenylsubstituierten Bis(amino)gallanen

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Die vorliegende Arbeit behandelt die Untersuchung verschiedener mono- and disubstitutierter Gallylferrocene bzgl. ihrer Synthese und Struktur sowie der sich daraus ergebenden chemischen und physikalischen Eigenschaften. Das Bis(diaminogallyl)ferrocen [{Fe(eta 5-C5H4)2}{Ga(tmp)2}2] 8 und das monosubstitutierte Gallylferrocen [{(eta 5-C5H5)Fe(eta 5-C5H4)}{Ga(tmp)2}] 9 erwiesen auf Grund ihrer einfachen Synthese sich als die am besten geeigneten Startmaterialien zur Synthese von anderen gallyl-substitutierten Ferrocenen und Gallaferrocenophanen. Zudem wurden zwei weitere gallyl-substitutierte Ferrocene [{Fe(eta 5-C5H4)2}{Ga{N(SiMe3)2}2}2] 10 und [{(eta 5-C5H5)Fe(eta 5-C5H4)} {Ga{N(SiMe3)2}2}] 11 erhalten. Bei der Reaktion von 8 und 9 mit unterschiedlichen Säuretypen wurden verschiedene Reaktionsweisen beobachtet. Die Behandlung von 8 und 9 mit einprotonigen Säuren wie Essigsäure, Ethanol oder Phenol ergab die gallyl-substitutierten Ferrocene 14 – 17 und 20 – 22. Die so erhaltenen neuen gallyl-subtituierte Ferrocene wurden durch Protonierung und Abspaltung der tmp-Gruppen an den Gallium-Atomen gebildet. Dies sind [tmpH2]+2[{Fe(eta 5-C5H4)2}{Ga(O2CMe)3}2]2- 14 und [tmpH2]+[{(eta 5-C5H5)Fe(eta 5-C5H4)} {Ga(O2CMe)3}]- 20, [tmpH2]+2[{Fe(eta 5-C5H4)2}{Ga(O-C6H5)3}2]2- 16, [Li(thf)2]+2[{Fe(eta 5-C5H4)2}{Ga(O-C6H5)3}2]2- 17, [tmpH2]+[{(eta 5-C5H5)Fe(eta 5-C5H4)} {Ga(O-C6H5)3}]- 21, [Li(thf)2]+[{(eta 5-C5H5)Fe(eta 5-C5H4)}{Ga(O-C6H5)3}]- 22 und [{Fe(eta 5-C5H4)2}{GaOEt}2O]4 15. Die Reaktion von 8 oder 9 mit organischen Disäuren wie Malonsäure und Catechol führte unter Spaltung sowohl der GaN- als auch der GaC-Bindungen zu [tmpH2]+3[{CH2(COO)2}3Ga]3- 18 und [tmpH2]+2[(sigma-C6H4-O2)2Ga(OC6H4OH)]2- 19. Lässt man 8 mit Kohlenstoffdioxid reagieren, bildet sich unter Insertion in die GaN-Bindungen das Carbaminat [{Fe(eta 5-C5H4)2}{Ga(O2Ctmp)(µ2-O2Ctmp)}2] 13.

Translation of abstract (English)

In this work, several mono- and disubstituted gallyl ferrocenes were synthesized and their chemical and physical properties have been investigated. In the same time, new information’s regarding the stability and atoms arrangement in solid state structures of a series of mono- and disubtituted ferrocenyl gallane are reported. From all of them, the disubstituted gallyl ferrocene [{Fe(eta 5-C5H4)2}{Ga(tmp)2}2] 8 and the monosubstituted gallyl ferrocene [{(eta 5-C5H5)Fe(eta 5-C5H4)}{Ga(tmp)2}] 9 proves to be the most suited starting material for the synthesis of other gallyl substituted ferrocenes and gallaferrocenophanes. That is because of their moderate to high yield syntheses. 8 and 9 have been characterized by means of 1H-, 13C-NMR spectroscopy, elementary analysis, mass spectrometry, cyclovoltammetry and single crystal X-ray analysis. Also, several quantum chemical calculations using the crystal coordinates of 8 and 9 gave an insight into their electronically structures and stabilities. Other two gallyl substituted ferrocenes [{Fe(eta 5-C5H4)2}{Ga{N(SiMe3)2}2}2] 10 and [{(eta 5-C5H5)Fe(eta 5-C5H4)}{Ga{N(SiMe3)2}2}] 11 have been synthesized. By the reaction of 8 and 9 with different acids, a different behavior could be observed. When 8 and 9 have been treated with monoacids as acetic acid, ethanol or phenol different gallylsubstituted ferrocenes 14 – 17 und 20 – 22 were obtained. These new gallylsubtituted ferrocenes are formed by cleavage of the Ga-N bonds. With acetic acid [tmpH2]+2[{Fe(eta 5-C5H4)2}{Ga(O2CMe)3}2]2- 14 and [tmpH2]+[{(eta 5-C5H5)Fe(eta 5-C5H4)} {Ga(O2CMe)3}]- 20, with phenol [tmpH2]+2[{Fe(eta 5-C5H4)2}{Ga(O-C6H5)3}2]2- 16, [Li(thf)2]+2[{Fe(eta 5-C5H4)2}{Ga(O-C6H5)3}2]2- 17, [tmpH2]+[{(eta 5-C5H5)Fe(eta 5-C5H4)} {Ga(O-C6H5)3}]- 21 and [Li(thf)2]+[{(eta 5-C5H5)Fe(eta 5-C5H4)}{Ga(O-C6H5)3}]- 22 and with ethanol [{Fe(eta 5-C5H4)2}{GaOEt}2O]4 15 were formed. When 8 or 9 was reacted with the organic diacids malonic acid and catechol, not only the Ga-N bonds, but as well the Ga-C bonds were cleaved and [tmpH2]+3[{CH2(COO)2}3Ga]3- 18 and [tmpH2]+2[(sigma-C6H4-O2)2Ga(OC6H4OH)]2- 19 were obtained. The reaction of 8 with carbon dioxide leads to the formation of the carbaminate [{Fe(eta 5-C5H4)2}{Ga(O2Ctmp)(µ2-O2Ctmp)}2] 13.

Item Type: Dissertation
Supervisor: Prof. Dr. Linti, Gerald
Date of thesis defense: 18 July 2008
Date Deposited: 24 Jul 2008 15:17
Date: 2008
Faculties / Institutes: Fakultät für Chemie und Geowissenschaften > Institute of Inorganic Chemistry
Subjects: 540 Chemistry and allied sciences
Uncontrolled Keywords: gallium , gallylferrocene , gallaferrocenophane , X-Ray Struktur Analysegallium , gallyl ferrocene , galla ferrocenophane , X-Ray structure analysis
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