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Transition Metal Complexes of Porphyrin Analogs And TRANSITION METAL COMPLEXES OF PORPHYRIN ANALOGS AND BORATE-BASED COORDINATION COMPLEXES A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Anıl Çetin May, 2007 TRANSITION METAL COMPLEXES OF PORPHYRIN ANALOGS AND BORATE-BASED COORDINATION COMPLEXES Anıl Çetin Dissertation Approved: Accepted: Advisor Department Chair Christopher J. Ziegler Kim C. Calvo Committee Member Dean of the College Claire A. Tessier Ronald F. Levant Committee Member Dean of the Graduate School David A. Modarelli George R. Newkome Committee Member Date Wiley J. Youngs Committee Member Rex D. Ramsier ii ABSTRACT The synthesis of low-coordinate metal ions has been a focus of bioinorganic chemists due to their important roles in active sites in enzymes and protein. Although the isolation of these types of complexes is challenging, porphyrin analogs with one or two carbon atoms in the interior position can be good candidates for generating protected low coordinate metal sites. The metal coordination of one or two carbon substituted hemiporphyrazines, namely monocarbahemiporphyrazine and dicarbahemiporphyrazine, was investigated. These porphyrin analogs, in which one or two of the central metal binding nitrogen atoms were replaced with C-H groups, were synthesized in the early 1950s by Linstead and co-workers, but their metal binding chemistry remained unexplored. Several low coordinate metal complexes of dicarbahemiporphyrazine, namely silver, copper, manganese, iron and cobalt were synthesized. Three different cobalt complexes of monocarbahemiporphyrazine in +2 and +3 oxidation states were also synthesized. Porpholactone is another example of a ring modified porphyrin isomer. In this macrocycle one of the four pyrrollic units is oxidized to an oxazolone ring. Metal complexes of porpholactone may be novel catalysts for epoxidation of alkenes. The synthesis and X-ray crystal structure of first manganese complex of the porpholactone 5,10,15,20-tetraphenylporpholactone are reported. The catalytic activity of the complex iii by using a variety of substrates was explored and it was compared with that of manganese tetraphenylporphyrin. Metal complexes of a sulfur containing borate-based chelating ligand, - tris(imazolyl)borate, HB(mt)3 were examined. Three different modes of interaction were observed with divalent closed d shell metal metal cations: Ca(II), Ba(II) and Hg(II). This study exhibits the diversity of binding not typically observed in the scorpionate family. - With group II and group XII metals, the HB(mt)3 ligand can act as a non-coordinating anion, can engage in B-H agostic bonding, and can form metal cluster compounds. Molecular organization of guest molecules within nanometer-sized structures is a big challenge in terms of controlling the physical properties and chemical reactivities. In our group, we are investigating borate-based coordination polymer, lead tetrakis(imidazolyl)borate, to organize and sequester anionic guests. A variety of anionic guests were organized within the layers lead(II) borate scaffolds. The possibility of topochemical polymerization of these pre-organized anionic monomers in the crystalline state was explored. iv DEDICATION To my parents Nurhan and Güney Çetin… Bu tez annem Nurhan Çetin ve babam Güney Çetin’e adanmıştır. Dünyaya çocuk getirmenin sorumluluğunu en iyi bilen ve şu an bu tezi yaziyor olmamın yegane nedeni olan iki insana…Hayatta başıma ne gelirse gelsin, dünyanın neresinde olursam olayım arkamda o iki insanin olduğunu bilmenin güvenini bana yaşatan anneme ve babama… Size bütün bunlar için ve bugüne kadar bana gösterdiğiniz sevgi, özveri, çaba ve sabır için teşekkür etmenin ne kadar yetersiz olduğunun farkındayım. Umarim size layık bir evlat olabiliyorumdur. v ACKNOWLEDGEMENTS The past five years of my life has not been easy; being miles away from my beloved ones, expressing myself in a foreign language, trying to adapt to a new culture and of course being a graduate student in chemistry department. But what I am sure is if I had another chance to return to five years back from now, I would again choose to come here. And it is because of the things I have learned through my graduate work, the wonderful people I have met and the countless memories I have shared. I am thankful to you all. First of all, I would like to thank my advisor, Dr. Christopher Ziegler. There is no need to mention the impossibility of writing this thesis without you. Thanks for the support, the guidance and at the same time the freedom you have given me. Thanks for believing in me even at the times that I did not believe in myself. Many thanks to my parents, Nurhan and Güney Çetin, brother Mert and sister-in-law Özün and my grandparents for the love, guidance and support. Thanks for being there whenever I need someone, thanks for giving me the comfort of having people who care about me and of course traveling that many miles just to visit me. It is wonderful to have you all. To my former research lab mates Janet Shaw, John Harvey, Barton Hamilton, and Tang Ding, thank you for the helpful discussions and the memories we have shared. Thanks for making me feel like I am home, helping me to find my way in the laboratory vi and helping me to improve my language skills. Also thanks to the new group members Saovalak Sripothongnak, Natalie Barone and Roshinee Costa for the friendship and for your friendly support. Finally, thank you Semih. You are the reason why I am here today; it is your love that brought me here to America. Your love, patience and support helped me go through all the problems I have gone through these past years. And now another chapter of our lives is ending and we are getting ready for a new start. I am not sure where our next stop is going to be or what we are going to be doing next year these times, but what I am sure is that we are going to be together. vii TABLE OF CONTENTS Page LIST OF TABLES………………………………………..…………………..…….…......x LIST OF FIGURES……………………...…………………………………………...….xii LIST OF SCHEMES…………………...………………………..…………………...….xx LIST OF ABBREVIATIONS…………...…………………………..……………….…xxi CHAPTER I. INTRODUCTION TO ORGANOMETALLIC CHEMISTRY OF PORPHYRINOIDS IN EQUATORIAL PLATFORM…………………..…..………..1 N-confused porphyrins…..…………..……………………………….…................7 σ-type M-C bonding...........................................................………………………10 Divalent metal complexes of NCP with M-C bonds..............................................10 Trivalent metal complexes of NCP………....………….........................................23 Side-on M···H-C interaction....................................................................................33 Monomeric metal complexes of NCP.....................................................................34 Dimeric metal complexes of NCP..........................................................................38 Carbaporphyrinoids.................................................................................................48 II. METAL MEDIATED C-H BOND ACTIVATION IN A CARBON SUBSTITUTED HEMIPORPHYRAZINE.......................……………...….….....….88 Experimental..................................................................………………………...90 viii Results and Discussion ............................................……………………………94 III. COMPLEXES OF LOW-COORDINATE MIDDLE TRANSITION METAL DICARBAHEMIPORPHYRAZINE........................................................113 Experimental.................................................................………………………..114 Results and Discussion ............................................…………..………………117 IV. COORDINATIVE Co(II) AND Co(III) COMPLEXES OF MONOCARBAHEMIPORPHYRAZINE...............................................................127 Experimental.................................................................………………………..128 Results and Discussion ............................................…………..………………131 V. STRUCTURE AND CATALYTIC ACTIVITY OF A MANGANESE(III) TETRAPHENYLPORPHOLACTONE...................................................................140 Experimental.................................................................………………………..142 Results and Discussion ............................................…………..………………145 VI. COMPLEXES SUMMARY OF THE COORDINATION CHEMISTRY OF PORPHYRIN ANALOGS.......................................................................................151 VII. COORDINATIVE FLEXIBILITY IN HYDROTRIS(IMAZOLYL)BORATE DIVALENT METAL COMPOUNDS...................................................................154 Experimental.................................................................………………………..156 Results and Discussion ............................................…………..………………160 VIII. INVESTIGATING THE TOPOCHEMICAL POLYMERIZATION OF ANILINE DERIVATIVES IN Pb(II) BORATE SCAFFOLDS.....................167 Experimental.................................................................………………………..170 Results and Discussion ............................................…………..………………176 REFERENCES...………………………………...…………………….………………188 ix LIST OF TABLES Table Page 2.1 Crystal data and structure refinement for dchp·HCOOH……..................... 95 2.2 Crystal data and structure refinement for [dchp]2·H2O.……………............ 96 2.3 Crystal data and structure refinement for dchp·2CH3CN.…………………. 97 2.4 Crystal data and structure refinement for dchp·2py....................................... 98 2.5 Crystal data and structure refinement for dchp·DMF
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