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Rhodium(Iii), and Iridium(Iii) Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1980 Cyclometallated Compounds of Palladium(ii), Rhodium(iii), and Iridium(iii). Michael Anthony Gutierrez Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Gutierrez, Michael Anthony, "Cyclometallated Compounds of Palladium(ii), Rhodium(iii), and Iridium(iii)." (1980). LSU Historical Dissertations and Theses. 3562. https://digitalcommons.lsu.edu/gradschool_disstheses/3562 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 was produced from a copy of a document sent to us for microfilming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand 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 you of complete continuity. 2. When an image on the film is obliterated with a round black mark it is an indication that the film inspector noticed either blurred copy because of movement during exposure, or duplicate copy. Unless we meant to delete copyrighted materials that should not have been filmed, you will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photo­ graphed the photographer has followed a definite method in “sectioning” the material. It is customary to begin filming at the upper left hand corner of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For any illustrations that cannot be reproduced satisfactorily by xerography, photographic prints can be purchased at additional cost and tipped into your xerographic copy. Requests can be made to our Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases we have filmed the best available copy. University Micrdrilms International 300 N. ZEEB ROAD, ANN ARBOR, Ml 48106 18 BEDFORD ROW, LONDON WC1R 4EJ, ENGLAND Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 8110416 GUTIERREZ, MICHAEL ANTHONY CYCLOMETALLATED COMPOUNDS OF PALLADIUM(II), RHODIUM(III), AND IRIDIUM(III) The Louisiana State University and Agricultural and Mechanical Col. PH.D. 1980 University Microfilms International300 N. Zeeb Road, Ann Arbor, M I 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CYCLOMETALLATED COMPOUNDS OF PALLADIUM(II), RHODIUM(III), AND IRIDIUM(III) 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 Department of Chemistry by Michael Anthony Gutierrez B.S., Manhattan College, 1972 December, 1980 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. To My Mother and In Memory of My Father ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENT The author wishes to express his deepest appreciation to the director of this research, Professor Joel Selbin, for his guidance and friendship during the past eight years. Sincere thanks are given also to Dr. George R. Newkome for his helpful discussions and friendship. The help and camarderie of his laboratory partner, Terry Roberie, is deeply esteemed. The author also wants to thank the following people for their assistance and friendship during his stay at Louisiana State University: Joe Sauer, Hellen Taylor, Veronica Majestic, Frank Fronczek, Leah Meade, Julie Bergeron Errol Olivier, James Medley, John Lightsey, Diane Sicks, and Daniel Church. The author also acknowledges the financial assistance received from Louisiana State University-Baton Rouge through a teaching assistantship and from the Dr. Charles E. Coates Memorial Fund of the Louisiana State University Founda tion for the publication of this dissertation. iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS P a g e ACKNOWLEDGEMENT...........................................iii LIST OF TABLES ........................................ v LIST OF F I G U R E S .......................................... vii ABSTRACT .............................................. xi INTRODUCTION .......................................... 1 A. General Introduction ........................... 1 B. Scope of the Present Research.... ............... 6 EXPERIMENTAL SECTION ................................. 12 A. Analytical Procedures ........................... 12 B. Materials........................................ 13 C. Reactions and Preparation of Complexes... ....... 22 RESULTS AND DISCUSSION ............................... 102 A. 2-Arylpyridines................................. 102 B. 2 ,6-Diarylpyridines, Benzo[h]quinoline, 5,6,8,9- Tetrahydrodibenz[c,h]acridine, and N-(2-Methoxy- benzylidine)aniline as Cyclometallating L i g a n d s .......................................... 149 C. Non-cyclometallated Compounds Involving Adduct or Salt Formation............................... 175 D. Attempted Reactions ............................. 187 SUGGESTIONS FOR FUTURE RESEARCH ....................... 189 REFERENCES ............................................ 191 VITA ................................................... 207 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES T a b le P a g e I. Attempted Reactions with Palladium(II) Compounds ...................................... 51 II. Attempted Reactions with Gold(I) and Gold(III) Compounds...................................... 54 III. Attempted Reactions with Transition Metal Compounds ....................... 57 IV. Reactions Attempted with Palladium(II) Complexes...................................... 60 V. Attempted Reactions with Gold and Rhodium C omplexes...................................... 62 VI. Yield, Melting Point, and Selected IR Data for Chloro-Bridged 2-Arylpyridine Palladium(II) Complexes (8) .................................. 105 VII. Yield, Melting Point, and Selected IR Data for Acetato-Bridged 2-Arylpyridine Palladium(II) Complexes ( 9 ) .................................. 113 VIII. 200 MHz NMR Data for Ligand and the Corresponding Acetato-Bridged Complex (9) .................... 122 IX. 200 MHz NMR Data for 2-(3'-nitrophenyl)pyridine and the Corresponding Cyclometallated Complexes of Palladium(II), Rhodium(III), and Iridium(III) 125 X. Yield, Melting Point, and Selected IR Data for Biscyclometallated Chloro-Bridged Dimers of Rhodium(III) and Iridium(III) ................. 135 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. T a b le P a g e XI. 200 MHz NMR Data for Rhodium(III) , Iridium(III), and Palladium(II) Cyclometallated Complexes . 137 XII. Yield, Melting Point, and Selected IR Data for Acetato-Bridged 2,6-Diarylpyridine Palladium(II) Complexes ( 1 4 ) ......................... 150 XIII. 200 MHz JH NMR Data for Acetato-Bridged 2,6- Diarylpyridine Palladium(II) Complexes (14) . 160 XIV. Yield, Melting Point, and Selected IR Data for Cyclopalladated Benzo[h]quinoline Complexes . 166 XV. *H NMR Data for Benzo[h]quinoline and Its Cyclometallated Complexes ....................... 167 vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF FIGURES Figure Page •v 1. The expanded NMR spectrum of 2-(3'-nitro- phenyl)pyridine in CDCI3 at 300°K in the 7.2 to 9.0 ppm region............................. 6A 2. The *H NMR spectrum of 5,6 ,8 ,9-tetrahydrodibenz- [c,h]acridine in CDCI3 at 300°K ............. 65 3(a). The NMR spectrum of 9e in CDCI3 at 300°K . 66 3(b). The expanded *H NMR spectrum of 9e in the 6.2 to 8.0 ppm region .......... 67 A(a). The *H NMR spectrum of 9f in CDCI3 at 300°K . 68 A(b). The expanded NMR spectrum of 9f in the 6.2 to 8.0 ppm region ........................... 69 5(a). The hi NMR spectrum of 9h in CDCI3 at 300°K . 70 5(b). The expanded NMR spectrum of 9h in the 6 .A to 8.2 ppm r e g i o n .............................. 71 6 (a). The 1H NMR spectrum of 9i in CDCI3 at 300°K , 72 6 (b). The expanded NMR spectrum of 9i in the 6 .A to 8.2 ppm region ........................... 73 7(a). The NMR spectrum of 9k in CDCI3 at 300°K . 74 7(b). The expanded JH NMR spectrum of 9k in the 6 to 8.5 ppm region ........................... 75 8 (a). The NMR spectrum of 91 in CDCI3 at 300°K . 76 8 (b). The expanded *H NMR spectrum of 91
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