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I. MATRIX ISOLATION of 1,1-DIAZENES II. DISTANCE, TEMPERATURE, and DYNAMIC SOLVENT EFFECTS on ELECTRON TRANSFER REACTIONS Thesis

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I. MATRIX ISOLATION of 1,1-DIAZENES II. DISTANCE, TEMPERATURE, and DYNAMIC SOLVENT EFFECTS on ELECTRON TRANSFER REACTIONS Thesis I. MATRIX ISOLATION OF 1,1-DIAZENES II. DISTANCE, TEMPERATURE, AND DYNAMIC SOLVENT EFFECTS ON ELECTRON TRANSFER REACTIONS Thesis by James Edward Hanson In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy California Institute of Technology Pasadena, California 1990 (Submitted September 8, 1989) 11 © 1990 James Edward Hanson All rights Reserved ill Acknowledgements I would like to thank my advisor, Peter Dervan , for his enthusiasm and support during my studies at Caltech. I would also like to thank Professor John Hopfield for his availability when I needed assistance with the theoretical complexities of the electron transfer work. I am deeply indebted to Lutfur "Zeta" Khundkar and Joe Perry for their expert assistance and collaboration in making measurements and understanding the implications of the results. Al Sylwester was extremely helpful in my first year as I began to work on 1,1-diazenes, and Alvin Joran and Burt Leland made my transition to the electron transfer project relatively simple. I should also thank those in the Dervan group who helped me with synthetic problems, especially John Griffin and Warren Wade. I appreciated discussions with some of the electron transfer experts at Caltech: Professor Rudy Marcus, Dave Beratan, Jose Onuchic, Dave Malerba, and Tad Fox. There were many times when the men in the chemistry shops provided invaluable assistance--you guys are the best! There are many who made my stay at Caltech enjoyable--I'll remember skiing with John and Linda Griffin and Heinz Moser, basketball (and marathons!) with Dave Kaisaki, tennis with Erich Uffelmann, and late night conversations with Kevin Luebke. There are also many outside Caltech who helped me keep a (tenuous) grip on reality. I appreciated weekends at the beach with Mike and Cathy Constantz or my cousins Jeff and Elizabeth Light. I am also grateful for the friendship of Ranjit Bhaskar, Joyce Stinson, Steve Burns, Dave Blakkolb, Bill Edmund, and many others. Finally, I must thank my parents for their love and support. IV Abstract Part I: Investigations of the reactive intermediates known as 1, 1-diazenes or aminonitrenes are reported. These unstable species were generated by UV photolysis of appropriately substituted carbamoyl azides under matrix isolation conditions. Four systems were investigated: three cyclic dialkyl 1,1-diazenes (1,1-tetramethylene­ diazene 1, 1, 1-trimethylenediazene 2, and 3,4-dehydro-1, 1-tetramethylenediazene 15) and the first diaryl 1,1-diazene, 1,1-diphenyldiazene 22. 1,1-Diazene 1 could be generated by broad band UV photolysis (200-400 nm) of the carbamoyl azide, but 2 and 22 required narrow band photolysis (290-310 nm) and gave poorer yields. 1, 1-Diazene 15 could not be isolated even at 10 K. The chemical and spectroscopic properties of the 1, 1-diazenes were investigated in some detail, and the results were analyzed with regard to the stability of the various 1,1-diazenes and the different reactive pathways available to 1,1-diazenes with different substituents. Part II: The dependence of intramolecular electron transfer rates for porphyrin-quinone compounds on distance and temperature was studied. It was found that the rates depend exponentially on the edge-to-edge donor acceptor distance Re as kET = ko exp [ -a. Re] with a. values of 1.10 to 1.25 in different solvents. The temperature dependence studies revealed that the electron transfer rates are not activated in a classical sense, but instead depend on the dynamic relaxation properties of the solvent. In 2- methyltetrahydrofuran, the rates are nearly independent of temperature at high temperatures (200-300 K), then begin to decrease with decreasing temperature. In toluene, the rates increase with decreasing temperature, while in deuterated toluene the rates initially increase with decreasing temperature, then go through a maximum v around 215 K, and finally decrease. Apart from the unusual solvent isotope effect in the toluene and toluene-ds data, this appears to be the first observation of the rate turnover with solvent "friction" predicted by Kramers. The results were analyzed in terms of theoretical predictions of the dependence of electron transfer rates on the longitudinal relaxation time of the solvent 'tL using the equation kNA kET =----a------ 1.00 + k +ykNA tL NA tL where kNA is a maximum rate and a and y are fitted parameters. This equation gave reasonable fits to the data for all three solvents. Vl Table of Contents List of Figures ...................................................................................... ix List of Tables ....................................................................................... xvi Part I. Matrix Isolation of 1,1-Diazenes .................................................... 1 Chapter 1. Introduction: 1,1-Diazenes .......................................................... 2 A. Chemistry of 1,1-Diazenes ........................................................ 4 B. Theoretical Studies ................................................................ 14 C. Direct Studies of 1,1-Diazenes .................................................. 18 1. Persistent 1,1-Diazenes .................................................... 18 2. 1,1-Diimide: Matrix Isolation of a 1,1-Diazene ......................... 25 3. Simple Dialkyl 1,1-Diazenes .............................................. 26 4. Other Experimental Studies ............................................... 31 Chapter 2. Cyclic Dialkyl 1, 1-Diazenes ........................................................ 34 A. Synthesis ........................................................................... 37 B. 1, 1-Tetramethylenediazene ....................................................... 38 1. FTIR Studies ................................................................ 38 2. Electronic Spectroscopy ................................................... 51 3. Product Analysis ........................................................... 54 4. Kinetics and Mechanism ................................................... 55 C 1,1-Trimethylenediazene ......................................................... 60 1. FTIR Studies ................................................................ 60 2. Electronic Spectroscopy ................................................... 75 3. Product Analysis ........................................................... 77 4. Kinetics and Mechanism ................................................... 80 Vil D. 3, 4-Deh ydro-1, 1-tetrameth y lenediazene ....................................... 8 3 1. Synthesis .................................................................... 84 2. FTIR Studies ................................................................ 85 3. Product Analysis ........................................................... 94 Chapter 3. 1, 1-Diphenyldiazene .................................................................. 95 A. FTIR Studies ....................................................................... 98 B. Electronic Spectroscopy and Product Analysis ............................... 114 Chapter 4. Conclusions ......................................................................... 117 Chapter 5. Experimental Section .............................................................. 124 Appendix. GVB Calculations on 1,1-Diazenes and Azomethinimines .................... 140 A. 1,1-Diazene Tautomerization .................................................... 141 B. Electrophilic 1,1-Diazenes ...................................................... 143 References and Notes ............................................................................ 146 Part II. Distance, Temperature, and Dynamic Solvent Effects on Electron Transfer Reactions ................................................................. 155 Chapter 6. Introduction : Electron Transfer ................................................... 156 A. Theory ............................................................................. 157 B. Experimental Studies ............................................................ 170 1. Biological Electron Transfer .............................................. 170 2. Electron Transfer in Synthetic Systems ................................ 17 5 3. Previous Studies on Rigid Porphyrin-Quinone Compounds ......... 182 Chapter 7. Distance Dependence of Electron Transfer ...................................... 190 A. Synthesis .......................................................................... 191 B. Electron Tran sfer Rates ......................................................... 196 Chapter 8. Temperature Dependence of Electron Transfer and the Role of Solvent Dynamics ................................................................... 209 Vlll A. Temperature Studies ............................................................. 211 Chapter 9. Conclusions ......................................................................... 238 Chapter 10. Experimental Section .............................................................. 240 References and Notes ............................................................................ 257 1X List of Figures Chapter 1 Figure 1. Generation and reactions of 1, 1-diazenes. Figure 2. Calculated energies of low lying electronic states of 1, l-diimide.23 Figure 3. Partial reaction coordinate diagram for diethyldiazene systems.29 Figure 4. Electronic absorption and emission spectra of 1, 1-diazene xxiv in CFCl3 at -78° C and -196° C respectively. 36 Figure 5.
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