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Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior Towards Cobalt and Iron Carbonyl Compounds

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Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior Towards Cobalt and Iron Carbonyl Compounds Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior towards Cobalt and Iron Carbonyl Compounds von der Fakultät für Naturwissenschaften der Technischen Universität Chemnitz genehmigte Dissertation zur Erlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) Vorgelegt von M.Sc. Grzegorz Paweł Filipczyk Geboren am. 07.01.1966 in Chorzów (Polen) eingereicht am: 31.05.2017 Erstgutachter: Prof. Dr. Heinrich Lang Zweitgutachter: Prof. Dr. Klaus Stöwe Tag der Verteidigung: 04.12.2017 ii Bibliografische Beschreibung und Referat Filipczyk, Grzegorz Paweł Ferrocenyl-Alkine und Butadiine: Reaktionsverhalten gegenüber Cobalt- und Eisencarbonyl-verbindungen Technische Universität Chemnitz, Fakultät für Naturwissenschaften Dissertation, 2017, 155 Seiten. Die vorliegende Dissertation beschreibt die Synthese und Charakterisierung von neuartigen perferrocenylierten, cyclischen Komplexen unter Anwendung der Cobalt- vermittelten Cyclomerisierung in Kombination mit einer C-H-Bindungsaktivierung als auch die Bildung von ferrocenylierten Phosphinoalkinid-Komplexen mit Eisen- und Cobaltcarbonylen. Die elektrochemischen Eigenschaften und die Elektronentransfer- prozesse zwischen den terminalen Ferrocenyleinheiten in den unterschiedlichen cyclischen Verbindungen wurden unter Einbeziehung der Struktur/chemischen Zusammensetzung der Brückenbausteine ermittelt. Elf perferrocenylierte, cyclische Komplexe wurden mittels [2+2] bzw. [2+2+2] 5 5 Cyclomerisierung von 1,4-Diferrocenylbutadiin FcC≡C–C≡CFc (Fc = Fe(η -C5H4)(η - 5 C5H5)) unter Verwendung von Dicarbonylcyclopentadienylcobalt Co(η -C5H5)(CO)2 erhalten. Diese können in drei Gruppen unterteilt werden: (i) Produkte der Cyclodimerisierung mit zusätzlicher Kettenverlängerung, welche Cyclobutadienyl- einheiten als zentrale Brückenbausteine besitzen (3a,b und 4a,b), (ii) Produkte der Cyclodimerisierung mit gleichzeitiger CO-Insertion (6a,b,c und 7), und (iii) Produkte der Cyclotrimerisierung gefolgt von einem Ringschluss durch eine C-H-Bindungsaktivierung (5a,b,c). Die Optimierung der Reaktionsbedingungen wurde zur Ausbeutemaximierung der jeweiligen Verbindungsfamilien durchgeführt. Ein weiterer Teil dieser Forschungsarbeit bezieht sich auf die verschiedenen Reaktionsmuster von (Ferrocenylethinyl)diphenylphosphan- mit zweikernigen Eisen- bzw. Cobaltcarbonylverbindungen in Form von Dieisennonacarbonyl und Dicobaltoctacarbonyl als Reagenzien. Dabei konnten sechs gemischte Carbonyl- und Ferrocenyl-funktionalisierte Phosphinoacetylid-Komplexe mit Eisen(0) und Cobalt(0) erhalten und charakterisiert werden. Stichworte: Eisen, Cobalt, Ferrocenyl, Alkin, Cyclisierung, C–H Aktivierung, Eisencarbonyl, Cobaltcarbonyl, Phospinoalkin, P–C Bindungsspaltung, Elektrochemie, Spektro- Elektrochemie iii Abstract Filipczyk, Grzegorz Paweł Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior towards Cobalt and Iron Carbonyl Compounds Technische Universität Chemnitz, Fakultät für Naturwissenschaften PhD Thesis, 2017, 155 Pages The present PhD study focuses on the synthesis and characterization of novel perferrocenylated cyclic complexes utilizing cobalt - mediated cyclomerization in combination with C–H bond activation as well as formation of ferrocenylated phosphino- alkyne compounds with iron and cobalt carbonyls. Electrochemical properties and electron-transfer processes between terminal ferrocenyl units in the diverse cyclic compounds are explored in relation to the chemical composition of the building blocks connecting them. Eleven perferrocenylated cyclic compounds were obtained via [2 + 2] and [2 + 2 + 2] 5 5 cyclomerization of 1,4-diferrocenylbutadiyne FcC≡C–C≡CFc (Fc = Fe(η -C5H4)(η -C5H5)) 5 by the reaction with dicarbonylcyclopentadienylcobalt Co(η -C5H5)(CO)2. They are subdivided into three groups: (i) products of cyclodimerization with additional chain extension, possessing cyclobutadienyl moieties as a central linkage unit (3a,b and 4a,b), (ii) products of cyclodimerization with consecutive CO insertion (6a,b,c and 7), and (iii) products of cyclotrimerization followed by cycle formation via C–H bond activation (5a,b,c). Optimization of the reaction conditions was made in order to maximize the amount of each group of compounds. Furthermore, another part of this research work focuses on diverse reaction patterns of (ferrocenylethynyl)diphenylphosphane with diironnonacarbonyl and dicobaltocta- carbonyl. Six mixed carbonyl and ferrocenyl-functionalized phospinoalkynyl compounds of iron(0) and cobalt(0) were obtained and characterized. Keywords: Iron, Cobalt, Ferrocenyl, Alkyne, Cyclization, C–H Activation, Iron Carbonyl, Cobalt Carbonyl, Phospinoalkyne, P–C Bond Cleavage, Electrochemistry, Spectro- electrochemistry. iv Ort und Zeitraum der Durchführung Die vorliegende Promotionsarbeit wurde in der Zeit von November 2010 bis Mai 2017 unter Leitung von Herrn Prof. Dr. Heinrich Lang am Lehrstuhl für Anorganische Chemie der Technischen Universität Chemnitz durchgeführt. Herrn Prof. Dr. Heinrich Lang danke ich für die gewährten Freiheiten bei der Bearbeitung des Themas, die anregenden Diskussionen sowie für die großzügige Unterstützung dieser Arbeit und das mir entgegengebrachte Vertrauen. v Widmung Dem liebenden Gott, meinen Eltern und denen, die mit mir den Weg gegangen sind vi Präambel Im Rahmen der Promotionsarbeit an der Professur Anorganische Chemie der Technischen Universität Chemnitz konnten drei Publikationen erstellt werden. Diese sind bereits veröffentlicht. Alle Publikationen wurden unter Anleitung von Herrn Prof. Dr. Heinrich Lang und Dr. A. Hildebrandt selbstständig und in englischer Sprache verfasst. Im Falle von Publikationen, welche in arbeitsgruppeninterner Kooperation erstellt wurden, wird an entsprechender Stelle verwiesen. Die Zusatz - Informationen (Supporting Information) können auf den entsprechenden Internetseiten der Journale eingesehen werden. Alle diese Promotionsschrift betreffenden Manuskripte sind in inhaltlich unveränderter Form als Kapitel C, D und E eingefügt worden. Die Zusammenfassungen dieser sind im Kapitel F als Anhänge A-C wiedergegeben. Die Kurzfassungen und Danksagungen sind als Anhänge D-F beigefügt. Die Kapitel A Einleitung (Introduction), Kapitel B Kenntnisstand (State of Knowledge) und Kapitel F Zusammenfassung (Summary) sowie die Abschnitte Inhaltsverzeichnis (Table of Contents), Abkürzungen (List of Abbreviations) und Anhang (Appendix) sind in englischer Sprache erstellt worden. Weiterhin erfolgt die Nummerierung der in der Dissertationsschrift aufgeführten chemischen Verbindungen gemäß der Bezeichnung des Manuskriptes, in welchem die wissenschaftlichen Ergebnisse veröffentlicht wurden. vii Table of contents Bibliografische Beschreibung und Referat ...................................................................... iii Abstract ................................................................................................................................. iv Ort und Zeitraum der Durchführung ................................................................................. v Widmung ............................................................................................................................... vi Präambel .............................................................................................................................. vii List of Abbreviations .......................................................................................................... xii CHAPTER A Introduction ................................................................................................ 15 References ........................................................................................................................... 16 CHAPTER B State of Knowledge .................................................................................... 19 1 (Spectro)electrochemical studies of mixed-valent transition metal complexes. Theoretical background .................................................................................................... 19 1.1 Mixed-valent compounds – classification .............................................................. 20 1.2 Spectroelectrochemistry ........................................................................................ 21 1.3 Electrochemistry..................................................................................................... 25 2 (Di)ferrocenylalkynes – synthesis and reactions ................................................... 28 2.1 1,4-Diferrocenylbutadiyne ..................................................................................... 29 2.2 Other (poly)ferrocenyl substituted alkyne derivatives ......................................... 35 3 Dicarbonylcyclopentadienylcobalt – [2+2] and [2+2+2] cyclo-addition reactions 37 3.1 [2+2] and [2+2+2] cycloaddition – cyclobutadiene, cyclopentadienone, benzene and pyridine based systems .............................................................................................. 38 3.2 Mechanism of [2+2] and [2+2+2] cycloaddition/cyclization and [2+2] cycloaddition/cyclization with CO insertion mediated by CoCp(CO)2 ............................ 40 4 Chelation-assisted C–H bond activation mediated by cobalt species ................... 42 5 Phosphinoalkynes and their reaction with iron and cobalt carbonyls ................ 44 5.1 Mechanism of the P–C(sp) bond cleavage in phosphinoalkynes ............................. 48 6 Complexes setup by (ferrocenylethynyl)diphenylphosphane .............................. 50 References ..........................................................................................................................
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