Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1984 A Study of Aromatic Amine N-Oxide Complexes of Group IIia Metal Alkyls. Ronald Dale Snelling Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Snelling, Ronald Dale, "A Study of Aromatic Amine N-Oxide Complexes of Group IIia Metal Alkyls." (1984). LSU Historical Dissertations and Theses. 4030. https://digitalcommons.lsu.edu/gradschool_disstheses/4030 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. 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Zeeb Road Ann Arbor, Ml 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 8 5 1 5 1 5 4 Snelling, Ronald Dale A STUDY OF AROMATIC AMINE N-OXIDE COMPLEXES OF GROUP IIIA METAL ALKYLS The Louisiana State University and Agricultural and Mechanical Ph.D.Col. 1984 University Microfilms I nternâtiOnS!300 N. zeeb Road, Ann Arbor, Ml 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 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. 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A Study of Aromatic Amine N-oxide Complexes of Group IIIA Metal Alkyls A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Ronald Dale Snelling A.B., Drury College, 1976 December, 1984 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Dedicated to B. D. S. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENT The author would like to acknowledge the encouragement, the aid, and the advice that were provided by his major professor, Dr. B. Sen. A very special note of thanks is due my wife, Beth Snelling, for her years of work, understanding, and patience. Thanks is also due for her help in typing and proofreading the manuscript. The Charles E. Coates Memorial Fund of the LSU Foundation, donated by George H. Coates, is gratefully acknowledged for financial support. The Ethyl Corporation and the Reilly Tar and Chemical Corporation for their donation of chemicals used in this w o r k . Ill Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS PAGE ACKNOWLEDGEMENTS.......................................... il LIST OF TABLES............................................ viii LIST OF FIGURES.......................................... xi LIST OF ABBREVIATIONS USED IN TABLES................... XV ABSTRACT.................................................... xvi CHAPTER I. INTRODUCTION..................................... 1 II. EXPERIMENTAL..................................... 18 A. Inert Atmosphere Techniques............. 18 B. Starting materials......................... 19 1) Metal Alkyls.......................... 19 2) Metal Chlorides....................... 19 3) Solvents............................... 19 4) Ligands................................ 20 a) Pyr idine-N-oxide................. 20 b) 2-Picoline-N-oxide............... 20 c) 3-Picoline-N-oxide............... 20 d) 4-Picoline-N-oxide............... 20 C . Synthesis of Metal Alkyls................ 21 1) General Synthetic Procedure for Metal Alkyls........................ 22 a) Trimethylgallium................. 23 b) Tr iethylgallium.................. 24 c) Tr ipropylgallium................. 25 IV Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHAPTER PAGE d) Tributylgallium. .. 25 e ) Triisobutylgallium. 26 f ) Trimefhylindium. .. 27 g) Triethylindium..... 28 h) Tripropylindium.... 28 i) Tributylindium..... 29 j) Triisobutylindium.. 29 D. Synthesis of Metal Alkyl-Amine N-oxide Complexes............................... 31 1 ) General Synthetic Procedure for Metal Alkyl-Pyridine-N-oxide Complexes....................... 31 a Me?Al(PyO).. 32 b Et^Al(PyO).. 32 c Pr^Al(PyO).. 33 d Bu^Al(PyO).. 33 e i-BUgAlfPyO) 34 f Me^GafPyO).. 34 g Et-Ga(PyO).. 34 h Pr Ga(PyO).. 35 i Bu^Ga(PyO).. 35 j i-BUgGa(PyO) 36 k Me-In(PyO).. 36 1 Et^In(PyO).. 37 m Pr^In(PyO).. 37 n Bu_In(PyO).. 37 o 1 -■Bu^InCPyO) 38 2) General Synthetic Procedure for Metal Alkyl-2-picoline-N-oxide Complexes........................ 38 a Me_Al(2 -P ic O ).. 39 b EtTAl(2 -PicO ) . 39 c Pr^Al(2 -P icO ). 39 d Bu_Al(2 -P icO ) . 40 e i-Bu?Al (2-PicO) 40 f Me-Ga(2 -P icO ). 40 g Et^Ga(2 -P ic O ).. 41 h Pr^Ga(2 -P ic O ).. 41 i Bu^Ga(2 -P icO ). 42 j 1-1Su^Ga (2-PicO) 42 k Me ,In(2 -P ic O ).. 42 1 Et 3 l n (2 -P icO ) . 43 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHAPTER PAGE m) Pr-In(2-PicO) 43 n) Bu^In(2-PicO) 44 o) iU2ln(2-PicO) 44 3) General Synthetic Procedure for Metal Alkyl-3-picoline-N-oxide Complexes........................ 45 a ) Me ^A1 3-PicO)............. b) Et ::a i 3-PicO)............. ...... 45 c ) Pr Z^Al 3-PicO)............. d) Bu <A 1 3-PicO)............. ...... 46 e ) i-BuuAl(3-PicO)........... ...... 47 f ) MeqGa 3-PicO)............. ...... 47 q) Et ^Ga 3-PicO)............. h) Pr ^Ga 3-PicO)............. ...... 48 i) Bu ^Ga 3-PicO)............. ...... 48 i) i- BuuGa(3-PicO)........... ...... 49 k) Me-.In 3-PicO)............. 1 ) Et ]ln 3-PicO)............. m ) Pr ::in 3-PicO)............. ...... 50 n ) Bu :!in 3-PicO)............. ...... 50 0 ) dUgl n(3-PicO)........... ...... 51 4) General Synthetic Procedure for Metal Alkyl-4-picoline-N-oxide Complexes....................... 51 Me^Al(4 -PicO).. 51 Et^Al(4 -PicO) . 52 Pr^Al(4 -PicO). 52 BU 3 AK 4 -PicO) . 52 i-Bu^Al (4-PicO) 53 Me^Ga(4 -PicO). 53 Et^Ga(4 -PicO). 54 Pr_Ga(4 -PicO). 54 Bu^Ga(4 -PicO).. 54 i-Bu_Ga (4-PicO)