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Micrc5films International 300 N OXYGEN ATOM TRANSFER REACTIONS OF NICKEL AND PALLADIUM NITRO COMPLEXES. Item Type text; Dissertation-Reproduction (electronic) Authors SIMONDSEN, JEANNE CLARE. Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 29/09/2021 02:32:32 Link to Item http://hdl.handle.net/10150/184281 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 01'1 the reproduction is heavily dependent upon the quality of the material submitted. 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Zeeb Road Ann Arbor, MI48106 8223015 Simondsen, Jeanne Clare OXYGEN ATOM TRANSFER REACfIONS OF NICKEL AND PALLADIUM NITRO COMPLEXES The University of Arizona PH.D. 1982 University Microfilms Intern ati 0 nal 300 N. Zeeb Road, Ann Arbor, MI 48106 OXYGEN ATOM TRANSFER REACTIONS OF NICKEL AND PALLADI~1 NITRO COMPLEXES by Jeanne Clare Simondsen A Dissertation Submitted to the Faculty of .the DEPARTMENT OF CHEllISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 1 982 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE As members of the Final Examination Committee, we certify that we have read the dissertation prepared by ---------------------------------------------Jeanne Clare Simondsen entitled Oxygen Atom Transfer Reactions of Nickel and Palladium Nitro Complexes and recomnlend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy Date Date IJfo, Jj /~i~ Date ) IJ 1£1<. Date2l24j Final approval and acceptance of this dissertation is contingent upon the candidate's submission of the final copy of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. lssertatlon Dlrector STATEHENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at the University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reprod~c­ tion of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgement the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. _. SIGNED: (7 . For my parents and For Royce iii ACKNOWLEDGMENTS I wish to express my gratitude to Dr. Robert D. Feltham, my research director, for his encouragement and advice during the course of this research. I also wish to thank Drs. J. H. Enemark and J. V. Rund for their helpful suggestions. Thanks are also due to my colleagues, Drs. Jules Dubrawski and Trevor Bailey for many helpful discussions both in and out of the laboratory. iv TABLE OF CONTENTS Page LIST OF ILLUSTRATIONS vii LIST OF TABLES ix ABSTRACT xi 1. BACKGROUND 1 2. PREPARATION AND CHARACTERIZATION OF COMPLEXES: THE CRYSTAL STRUCTURE OF Ni(N0 ) (NO) (PMe ) 2 ...•• 8 2 3 Introduction 8 Experimental • • • • • . •• .•••. • • • • 9 Preparation of Complexes . • • • . ••.•• 19 Collection and Reduction of X-Ray Intensity Data 20 Solution and Refinement of the Structure 20 Results and Discussion •• • • • • . • • . • • • • 23 Complexes of the Formula Ni(N02)2L2 • .• .. • • • 23 Complexes of the Formula Ni(N02) (NO)L2 ••••• 25 Structure of Ni(N02) (NO) (PMe3) 2 . 29 Description of Structure .~ 29 Structurar Interpretation • . 40 Conclusions . • • • • • • • • • 47 3. CRYSTAL STRUCTURES OF Ni(N02)2dppe AND [Ni(ONO)(NO)dppe]2 . 49 Introduction 49 Experimental • • • . • . • 50 Preparation of Complexes . • • • • • • • • • . 51 Collection and Reduction of X-Ray Intensity Data 51 Solution and Refinement of Structures . • • . • . 52 Results and Discussion • . • • 57 Description of Structures . • • • 57 Structural Interpretation • 73 4. NECHANISTIC STUDIES OF THE REACTION OF Ni(N02)2L2 AND CO 75 Introduction • • . • . 75 Experimental 76 Kinetic Studies • . 77 Isotope Scrambling Experiments 79 31p{lH} NMR Studies . 80 v vi TABLE OF CONTENTS--Continued Page Reversibility and Turnover Experiments 81 Detection of Intermediates • • • . 81 Results and Discussion . • • • • . • • • 82 5. REACTION OF PALLADIUM NITRO COMPLEXES WITH CO • 98 Introduction . 98 Experimental • • • • • • • • • 99 Collection and Reduction of X-Ray Intensity Data 99 Solution and Refinement of Structure • • • • • 100 Results and Discussion 102 APPENDIX A: LIST OF ABBREVIATIONS • • • • • 1· 117 REFERENCES . -. 118 LIST OF ILLUSTRATIONS Figure Page 1.1. Proposed pathway for the oxygen exchange reaction in CNMe 2 cis-Fe(N02)(NO)(S2 2)2 • .. ••• • . •• • ••• 1.2. Proposed mechanism for the reaction of NiC1 L with 2 2 NaN0 . • • • • • • • • . • • • . • • • • . • • 4 2 + 4 1.3. Proposed mechanism for dissociation of [Ni(NO)(PPh3)3] • 2.1. Mechanism proposed for oxygen atom transfer between N0 2 and CO • • • • • • • • • • • • • . • • • • • • 8 2.2. Correlation diagram relating the molecular orbitals of pseudotetrahedral four_coordinate NiNO 10 complexes of C and C symmetry showing allowed electronic 3 tranSl.tl.onsv .. s . " . • . 28 2.3. Perspective view and numbering scheme for Ni(N0 ) (NO) (PMe )2 2 3 at 135 K . .. .. .. 34 2.4. Perspective view and numbering scheme for Ni(N02) (NO) (PMe3) 2 at 293 K . 35 2.5. Packing diagram for Ni(N0 ) (NO) (PMe ) 2 at 293 K (A) and 2 3 135 K.(B) • • •••• '0' • • •• ••• 38 o 2.6. Ni-N (A) vs Ni-N-O angle (deg) for structurally characterized {NiNO}lO complexes . • • • • . • • • • • • . • 42 2.7. Correlation diagram relating the molecular orbitals of pseudo tetrahedral four-coordinate NiNO 10 complexes of C3v and Cs symmetry to those of four-coordinate square planar {NiNO}lO complexes of Cs symmetry 44 2.8. N-Ni-X angles for Ni(NO) (X) (PR )2 complexes. 46 3 . 3.1. Perspective view and numbering scheme for Ni(N02)2dppe 58 3.2. Perspective view and numbering scheme for [Ni(ONO)(NO)- dppe]2 . • • • • . • • . • . • • • 59 4.1. Modified spectrophotometer used for kinetic investigations • • • • . • . • . • . • . • . •• 78 v;ii viii LIST OF ILLUSTRATIONS--Continued Figure Page Beer's law plot for Ni(N0 ) (NO)dppe in CH C1 •...• 83 4.2. 2 2 2 ] 4.3. Plot of -In[(At -Am )/-Am vs t at 570 nm for the reaction of Ni(N02)2dppe with CO in CH C1 at 20°C •.••• 85 2 2 4.4. Dependence of kobsd on PCO for the reaction of Ni(N02)2dppe and CO at 20°C in CH C1 . • • . • • • . • • • 86 2 2 4.5. Scheme I: A mechanism proposed for the reaction of Ni(N02)2L2 anJ CO • . • • • . • • . •. • ••• 87 4.6. 31p{lH} nmr spectra of NiI2dppe (CDC1 3) under CO 89 4.7. 3lp{lH} nmr spectra of Ni(15N02)2dppe in CD C1 93 2 2 4.8. Experimental and simulated 31p{lH} nmr spectra of Ni(15NO Ni(15N02)2dppe in CD C1 at 220 K . • . • 94 2 2 4.9. 3lp{lH} nmr spectra of Ni(15 ) (15 )dppe in CD C1 • 95 N02 NO 2 2 4.10. Scheme II: An alternative mechanism proposed for the reaction of Ni(N02)2L2 and CO . • . • • • . • 96 5.1. Perspective view and numbering scheme for Pd (C0 )- 4 5 104 (PMePh2) 4 . • 5.2. Mechanistic implications of oxygen atom transfer via a nitrito isomer . • . • •• 115 5.3. Possible reaction routes for the formation of Pd4(CO)5L4 . • • . • •. • • • • • • • 116 LIST OF TABLES Table Page 2.1. Elemental analyses for Ni(N02)2L2 complexes •• 10 Eleffiental analyses for Ni(N0 ) (NO)L complexes 11 2.2. 2 2 Crystallographic data for Ni(N0 ) (NO) (PMe ) 2 ...•.••• 12 2.~. 2 3 2.4. N02 vibrational frequencies of Ni(N02)2L2 complexes ••••• 14 2.S.
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