Re(CO)3 TEMPLATE FORMATION OF DIIMINOISOINDOLINE BASED CHELATES A Dissertation Presented to The Graduate Faculty at The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Allen Jordan Osinski May 2018 Re(CO)3 TEMPLATE FORMATION OF DIIMINOISOINDOLINE BASED CHELATES Allen Jordan Osinski Dissertation Approved: Accepted: ___________________________ ___________________________ Advisor Department Chair Dr. Christopher J. Ziegler Dr. Christopher J. Ziegler ___________________________ ___________________________ Committee Member Dean of the College Dr. Claire A. Tessier Dr. John C. Green ___________________________ ___________________________ Committee Member Dean of the Graduate School Dr. Wiley J. Youngs Dr. Chand K. Midha ___________________________ ___________________________ Committee Member Date Dr. Yi Pang ___________________________ Committee Member Dr. Chrys Wesdemiotis ii ABSTRACT Over the last century, in the field of coordination chemistry, the number of template reactions has expanded into a diverse collection which can produce a variety of compounds. These template reactions have been used to afford compounds that would be difficult to obtain otherwise. One of the most famous template reactions is the synthesis of phthalocyanine, which was investigated by Linstead. After exploring the chemistry of phthalocyanine, Linstead synthesized hemiporphyrazines and bis(2- iminopyridyl)isoindolines from 1,3-diiminoisoindoline and various primary amines. Later, Siegl improved the synthesis of the hemiporphyrazines and the bis(2- iminopyridyl)isoindolines by employing a calcium ion as a templating agent. The template formation of isoindoline based macrocyclic compounds has been explored, however, the template formation of isoindoline based chelates is relatively unexplored. Due to its restrictive facial arrangement of carbonyl ligands and propensity to coordinate nitrogenous bases, the Re(CO)3-unit is a prime candidate for templating the formation of isoindoline based chelates. The second and third chapters in this thesis present the template synthesis of semihemiporphyrazines, “half” hemiporphyrazine like chelates, and α-amidino azadi(benzopyrro)methenes using the Re(CO)3-unit as a templating agent in a one-step reaction. In both cases, the complexes have terminal amine groups and do not experience hydrolysis as seen with the Re(CO)3-templated azadi(benzopyrro)methenes. Additionally, in the α-amidino azadi(benzopyrro)methene case, a rhenium bound nitrile is activated by a diiminoisoindoline unit to afford a rhenium bound amidine and one diiminoisoindoline sp2 carbon is converted to a sp3 carbon by attack of another diiminoisoindoline unit disrupting conjugation. The spectroscopy of the semihemiporphyrazines was investigated along with DFT and TDDFT calculations. Whereas, the conjugation in the α-amidino azadi(benzopyrro)methenes is disrupted resulting in yellow crystalline products that lack iii a metal-to-ligand charge transfer band. In the third chapter, 2,6-diacetylpyridine dihydrazone is coordinated to middle and late first row transition metals and their magnetic susceptibilities are explored via Evans NMR method. In the fourth chapter, neutral and deprotonated anionic complexes of the tetrakis(perfluorophenyl)-N-confused porphyrin are prepared and investigated by UV-visible and magnetic circular dichroism spectroscopies as well as by DFT and TTDFT calculation methods. iv ACKNOWLEDGEMENTS First of all, I would like to say thank you to my advisor Christopher J. Ziegler. Your support and leadership was an integral part of my journey through graduate school. Additionally, I would like to say thank you to my current and previous colleagues in lab. “Lab Mom” Ingrid took me in the first years of graduate school. I can’t say thank you enough to Kullapa and Ingrid for their patience and guidance during the first few years. Laura, Abed, Dan, and Briana- your friendship and support is greatly appreciated. Thank you to the members of my committee: Dr. Claire Tessier, Dr. Wiley Youngs, Dr. Yi Pang and Dr. Chrys Wesdemiotis. I am appreciative of your support and time spent serving on my committee. I would also like to thank the University of Akron and the department of Chemistry for accepting me into the program and financially supporting me during my Ph.D. career. Lastly, I would like to thank my family for putting up with me during the stressful times of graduate school and giving me the confidence to stay in school. Without their love and support, none of this would be possible. v TABLE OF CONTENTS LIST OF TABLES............................................................................................................viii LIST OF FIGURES.............................................................................................................ix LIST OF SCHEMES........................................................................................................xvii LIST OF ABBREVIATIONS...........................................................................................xix CHAPTER I. INTRODUCTION AND BACKGROUND......................................................................1 1.1 Template Reactions............................................................................................1 Phthalocyanine...................................................................................................6 Hemiporphyrazine............................................................................................15 Bis(2-iminopyridyl)isoindoline........................................................................32 “Helmet” and Bicyclic Phthalocyanines...........................................................46 1.2 Amidine Formation and Metal Mediated Nitrile and Activation.......................51 Re(CO)3 diimine complexes.............................................................................55 II. Re(CO)3-TEMPLATED SYNTHESIS OF SEMIHEMIPORPHYRAZINES...... ........62 Introduction............................................................................................................62 Experimental..........................................................................................................64 Results and Discussion...........................................................................................69 Conclusions............................................................................................................79 vi III. Re(CO)3-TEMPLATED SYNTHEIS OF α-AMIDINOAZADI(BENZOPYRRO)METHENES.......................................................80 Introduction............................................................................................................80 Experimental..........................................................................................................82 Results and Discussion...........................................................................................91 Conclusion...........................................................................................................106 IV. COMPLEXES OF 2,6-DIACETYLPYRIDINE DIHYDRAZONE WITH MIDDLE AND LATE FIRST ROW TRANSITION METALS.......................................................107 Introduction..........................................................................................................107 Experimental........................................................................................................109 Results and Discussion.........................................................................................122 Conclusion...........................................................................................................127 V. MAGNETIC CIRCULAR DICHROISM OF TRANSITION-METAL COMPLEXES OF PERFLUOROPHENYL-N-CONFUSED PORPHYRINS: INVERTING ELECTRONIC STRUCTURE THROUGH A PROTON...............................................128 Introduction..........................................................................................................128 Experimental........................................................................................................132 Results and Discussion........................................................................................133 Conclusions..........................................................................................................151 VI. SUMMARY...............................................................................................................152 REFERENCES................................................................................................................155 APPENDIX: PERMISSIONS ..........................................................................................183 vii LIST OF TABLES 2.1: X-ray crystal data and structure parameters for compounds 2.1-2.3............................68 2.2: X-ray crystal data and structure parameters for compounds 2.4 and 2.6......................69 3.1: X-ray crystal data and structure parameters for compounds 3.1-3.3............................89 3.2: X-ray crystal data and structure parameters for compounds 3.5-3.7............................90 3.3: X-ray crystal data and structure parameters for compounds 3.8-3.10..........................91 4.1: X-ray crystal data and structure parameters for compounds 4.1-4.3..........................117 4.2: X-ray crystal data and structure parameters for compounds 4.4-4.6..........................118 4.3: X-ray crystal data and structure parameters for compounds 4.7-4.8..........................119