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. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of “sectioning” the material has been followed. 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 illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. 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. U niversi^ M io m lm s International 300 N. Zeeb Road Ann Arbor, Ml 48106 8305306 Caste, Maureen Lynch TRANSITION METAL COMPLEXES OF POLYMER SUPPORTED MACROCYCLIC LIGANDS The Ohio State University Ph.D. 1982 University Microfilms I ntern atio n si 300 N. Zeeb Road, Ann Arbor, MI 48106 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 p ag es. 8. Print exceeds margin requirements _____ 9. Tightiy bound copy with print lost in spine ______ 10. Computer printout pages with indistinct print. 11. Page(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 n u mbered ___________ . Text fol lows. 14. Curling and wrinkled pages ______ 15. Other ______________________________________________________________ University Microfilms International TRANSITION METAL COMPLEXES OF POLYMER SUPPORTED MACROCYCLIC LIGANDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Maureen Lynch Caste, B.S., M.S. ***** The Ohio State University 1982 Reading Committee: Professor Daryle H. Busch Professor Devon W. Meek Professor Bruce E. Bursten Approved by: Advisor Department of Chemistry To my Korn and Dad ii ACKNOWLEDGMENTS My sincere thanks are extended to all members of Dr. Busch's research group, past and present, whose assistance and encouragement aided in the accomplishment of this work. Dr. Jeffrey Church and Dr. Judy Gallucci are specially noted for the solution of the crystal structure presented in this thesis and are thanked accordingly. As a long time friend and associate, I thank Dr. Randall J. Remmel who has been an Inspiration to me through his continuing encouragement and interest in my chemical career since I began my undergraduate degree. To end on a personal note, I would like to express the appreciation that I feel toward Mr. Jeffery C. Bricker for his deep insight in the area of chemistry, his encouragement of my pursuits, and his special friendship. But, above all, the most especial thanks are given to Dr. Daryle H. Busch for his support, both financial and emotional, his •j guidance in this work, and his friendship over the past three years. ill VITA November 30, 1954................ Born, Brooklyn, New York August, 1978 .................... B.S., University of Alabama in Birmingham Sept. 1978 - Dec. 1979 ......... Teaching Assistant, Department of Chemistry, The Ohio State Univ. Jan. 1980 - Oct. 1981 .... Research Associate, Department of Chemistry, The Ohio State Univ. October 1981 .................... M.S., The Ohio State University Columbus, Ohio Nov. 1981 - Sept. 1982 ......... Research Associate, Department of Chemistry, The Ohio State Univ. PUBLICATIONS Maureen Lynch Caste and Daryle H. Busch, ''Transition Metal Complexes of Polymer Supported Macrocyclic Ligands — Oxygen Binding and Oxygenation of Organic Substrates,'' 14th ACS Central Regional Meeting, Midland, Michigan, June 1982, Abstract 120. Sheldon G. Shore, Wen-Liang Hsu, Clemens R. Weisenberger, Maureen Lynch Caste, Melvyn Rowen Churchill, and Clifford Bueno, ''New Syntheses of Mixed Metal Clusters from HgOsa(CO)lo. Crystal and Molecular Structure of the Paramagnetic Cluster H 3 (n'-C5H 5 )CoOsa(CO), and Its Diamagnetic Structural Analogue H 3 (ri®-CsHs)Ni0 s3 (C0 ) 9 , " Organometalllcs. 1982, 1, 1405. FIELD OF STUDY Major Field: Chemistry Specialization — Inorganic Coordination Chemistry, Professor Daryle H. Busch, Advisor iv TABLE OF CONTENTS Page DEDICATION .......................................................... ii A C K N O W L E D G M E N T S .................................................... iii VITA ................................................................. iv LIST OF T A B L E S ........................................... vii LIST OF F I G U R E S ................................................... viii Chapter I. INTRODUCTION ............................................. 1 Polymer Supported Metals and Métal Complexes 1 Heme Protein Modeling 3 Polymer Supported Catalysts 17 Hydrogenations and Hydroformylations using Supported Catalysts 23 Selected Oxidation Reactions Using Supported Polymers 27 Complexes of Lacunar Ligands 43 Statement of the Problem 50 II. E X P E R I M E N T A L ............................................... 52 General Procedures 52 Physical Measurement 52 Synthesis of Nickel Complexes 54 Preparation of Ligand Salts 59 Synthesis of Cobalt Complexes 60 Preparation of the Supported Complexes 62 Adsorption of Cobalt(II) Complexes on Polymeric 6 8 Oxygen Exposure to the Polymer Samples 70 Polymer Reactions with Oxygen and Organic Substrates 71 V CONTENTS (CONT'D) III. CRYSTAL STRUCTURE AND PROPERTIES OF A NOVEL COBALT(II) COMPOUND CONTAINING FIVE COORDINATED NITROGENS, [Co{ (MeNIMINOETHYL) (MeNHETHYLDMea [l6]TETRAENENs }] (PFg) 2 73 Chemical Evidence for Pentadentate Chelation to the Cobalt(II) Species 77 Crystal Structure 85 Reaction of the Cobalt(II) Complex with Oxygen 97 IV. RESULTS AND D I S C U S S I O N .................................. 109 Model Studies 109 Chloromethylated Polystyrene 109 Poly(Vinylpyridine) 120 Controlled Pore Glass 122 Attachment of the Polymeric Supports 127 Covalent Attachment 127 Coordination Attachment 145 CFG Support 147 Reactions of the Polymer Supported Cobalt Complexes with Oxygen 152 Covalently Attached Complexes 152 Coordinately Attached Complexes 158 CPG Support 164 Reactions of Polymer Supported Complexes 166 Oxidation Catalysis 166 Gas Chromatographic Supports 171 APPENDIX A ........................................................ 178 APPENDIX B ..................................................... • 194 FOOTNOTES ........................................................ VI LIST OF TABLES Page Table 1. Materials Used to Support Metal Complexes ......... 2 2. NMR Peak Shifts for ICo{(MeN Iminoethyl)(MeN Ethi)Me2[16]-tetraene Ns}](PFe )2 in C D 3ON ......... 3. Summary of Crystallographic Data for C0 C 2 2 N 7H 3 2 P 2F 12 89 4. Bond Distances (A) and Angles (Deg)(B) with their Estimated Standard Deviations for C 0 C 2 2N 7H 3 2 P 3F 22 94 5. ‘h NMR Peak Shift for tCo{ (MeNIminoethyl)(MeNEthi)- M e 2 Ï16]tetraene N 5}](PF«) 2 , After Exposure to Oxygen, CDsCN Solvent, Room Temperature .................... 99 6 . NÈR Peak Shifts for ICo{MeNIminoethyl)(MeNEthi)- M e 2 [16]tetraene N-JlCPF*): After Exposure to Oxygen, CDaCN.Solvent ........................................ 99 7. NMR Assignments for [Ni{(NBz)2 (CHa)eMea[16]tetraene N 4 }](PFe) 2 in CDaCN, 80 MHz, 4 0 ° C ............... 118 8 . ^^C NMR Assignments for [Ni{(BzNMe)aMea[16]tetraene n J ] ( P F 6 > 2 in CDaCN, 8 MHz, 4 0 ° C .................. 120 9. Complexes Which have been Covalently Attached to Chloromethylated Polystyrene......................... 131 10. Analysis of Cobalt Complexes Covalently Attached to Chloromethylated Polystyrene ...................... 132 11. Lacunar Complexes which are Coordinatively Attached to Polymer Through Interaction with Pyridine Function 146 vii LIST OP FIGURES Figure Page 1. Methods of Attaching Complexes