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University Micrdrilms International 300 N INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1.The sign or “target” for pages apparently lacking from the document photographed is “Missing Page(s)”. If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. 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These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed. University Micrdrilms International 300 N. Zeeb Road Ann Arbor, Ml 48106 8400314 Wright, Bradford Barry I. PREPARATION AND CHARACTERIZATION OF META-XYLYLENE. SOLID STATE REACTIONS AND KINETICS OF ARYLCARBENES The Ohio State University Ph.D. 1983 University Microfilms International300 N. Zeeb Road, Ann Arbor, Ml 48106 Copyright 1983 by Wright, Bradford Barry All Rights Reserved PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages_______ 2. Colored illustrations, paper or print_______ 3. Photographs with dark background_______ 4. Illustrations are poor copy_______ 5. Pages with black marks, not original copy___ 6. Print shows through as there is text on both sides of _______page 7. Indistinct, broken or small print on several pages_______ 8. Print exceeds margin requirements_______ 9. Tightly bound copy with print lost in spine_______ 10. Computer printout pages with indistinct print_______ 11. P a g e (s) _____________ lacking when material received, and not available from school or author. 12. Page(s) _____________ seem to be missing in numbering only as text follows. 13. Two pages numbered______________ . Text follows. 14. Curling and wrinkled pages _______ 15. Other________________________________ _ ______________________________________________ University Microfilms International I. PREPARATION AND CHARACTERIZATION OF M-XYLYLENE II. SOLID STATE REACTIONS AND KINETICS OF ARYLCARBENES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Bradford Barry Wright, B.A. ****** The Ohio State University 1983 Reading Committee: Approved By Matthew S. Platz Leo A. Paquette David J. Hart Advisor Department of Chemistry To Julie VITA September 4, 1957. Born - Minneapolis, Minnesota 1979............ B.A., Honors, University of Oregon Honors College, Eugene, Oregon 1979............ Honorable Mention, National Science Foundation Graduate Fellowship Competition 1979-198 0........ Graduate Fellow, The Ohio State University, Columbus, Ohio 1980-198 1........ Graduate Teaching Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio 1981-198 2........ Graduate Research Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio. 1982-198 3........ Graduate Fellow, Phillips Petroleum, The Ohio State University, Columbus, Ohio PUBLICATIONS "Tunneling Parameters for the Hydrogen Atom Abstraction Reactions of Diphenylcarbene in a Low Temperature Matrix.", with V. P. Senthilnathan, Matthew S. Platz, and C. William McCurdy, Jr. Tetrahedron Lett. (1982), 23, 833-6. "Meta-Xylylene, Electron Spin Resonance Spectroscopy of the Triplet State.", with Matthew S. Platz J. Am. Chem. Soc. (1983), 105, 628-30. "Reactions of Triplet Diphenylcarbene by Hydrogen Atom Tunneling in Rigid Media.", with Matthew S. Platz, V. P. Senthilnathan, C. William McCurdy, Jr. J. Am. Chem. Soc. (1982), 104, 6494-501. FIELD OF STUDY Major Field: Organic Chemistry TABLE OF CONTENTS Page DEDICA TION........................................................................................................................... i i VITA.............................................. iii LIST OF TABLES..................................... V LIST OF FIGURES.................................... vii I. PREPARATION AND CHARACTERIZATION OF M-XYLYLENE 1 Historical Background........................ 2 Theoretical Background....................... 15 Results and Discussion....................... 26 Additional Studies on Biradicals.............. 50 II. SOLID STATE REACTIONS AND KINETICS OF TRIPLET ARYLCARBENES................................... 56 Historical Background........................ 57 Results and Discussion....................... 70 EXPERIMENTAL....................................... 133 APPENDIX 1......................................... 158 REFERENCES AND NOTES............................... 161 LIST OF TABLES Table Page 1. Heats of Formation of the Xylylenes.............. 10 2. Relative Energies of 8_ and 10.................... 11 3. Typical D'/hc Values for Biradicals.............. 25 k. Experimental Differences and Similarities Between Biradicals Derived from 21 and 25_........ ^0 5. Biradical Spectra from Diazocompounds............ 53 6. Biradical Spectra from Azides.................... 5^ 7. Product Distributions for the Reaction of Phenylcarbene with 2-Propanol as a Function of Temperature................................... 63 8. Arrhenius Parameters for Some Matrix Carbene Reactions................................ 68 9- Chemical and Kinetic Isotope Effects in the Reaction of Diphenylcarbene with Isotopically Labelled 2-Propanol at 77 K ......... 7*+ 10. Time Dependency of on Photolysis Time Interval.................................... 76 11 Concentration Dependence of 76 . Olio 12. Abbreviations Used for Carbenes Presented in the Remainder of Part II...................... 78 13. Carbene Rate Data in Toluene..................... 79 Ik. Arrhenius Parameters for the Reaction of Arylcarbenes with Various Solvent Matrices........................................ 8k 15. Calculated Eckart Barrier Parameters for Various Arylcarbenes in Toluene Matrices.......... 87 16. Carbene Rate Data in CCl^............ 10U v Table Page 17. Carbene Rate Data in Isotopically Labelled Methanols............................... 109 18. OH/CH Bond Insertion Product Ratios for Various Arylcarbenes in Isotopically Labelled Methanol Matrices at 77 K ............... 110 19. Signal Intensities in Arbitrary Units for Matched Tubes of Phenyldiazomethane in Isotopically Labelled Matrices................. 117 20. Signal Intensities in Arbitrary Units for Matched Tubes of Some Carbenes as a Function of Temperature in Toluene and Toluene-dg Matrices.............................. 118 21. Observed Maximum Splittings of Radical Generated by Reaction of Carbenes with Matrices........................................ 119 22. ESR Kinetic Data not Given in Text................ 1^0 23. ESR Signal Behavior of m-Xylylene as a Function of Temperature and Microwave Power........................................... l*tl 2k. Product Distribution Under Varied Experi­ mental Conditions for the Reaction of DPC with 2-Propanol.................................. 1^3 VI LIST OF FIGURES Figure Page 1. Apparatus for the Matrix Isolation of Xylylenes......................................... 9 2. Possible Combination of Benzyl and Methyl Radicals................................... 12 3. Possible Arrangements of Two Electrons In Two Orbitals................................... 15 k. States Obtained on Placing Two Electrons In Two Arbitrary Orbitals.......................... l6 5- Typical Biradical ESR Spectrum..................... 22 6. Coordinate System for the Spin Dipolar Interactions of Two Electrons.............. 22 7. ESR Spectrum of 22 in Low Field. ., ................ 27 8. ESR Spectrum of £5 in Ethanol at 77 K ............... 28 9. ESR Soectrum of £3 in Ether at 77 K .•........... 30 10. ESR Spectrum of 8_ in Ethanol-dg..................... 31 11. ESR Spectrum of 8^ in Methanol at 77 K ............... 32 12. ESR Spectrum of £3 in Toluene at 77 K ................ 33 13. ESR Spectrum of J3 in 2-Methyltetra- hydrofuran at 77 K ................................ 3^ lU. Thermal Generation of m-Xylylene................... 36 15. Biradical Spectrum Arising from Photolysis of Diphenyldiazomethane................
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