University of North Dakota UND Scholarly Commons Theses and Dissertations Theses, Dissertations, and Senior Projects January 2020 Substitution And Oxidation Reactions Of Cyclodiphosph(III)azane Compounds Of The Group 15 Elements Joseph Tabifor Musongong Follow this and additional works at: https://commons.und.edu/theses Recommended Citation Musongong, Joseph Tabifor, "Substitution And Oxidation Reactions Of Cyclodiphosph(III)azane Compounds Of The Group 15 Elements" (2020). Theses and Dissertations. 3113. https://commons.und.edu/theses/3113 This Dissertation is brought to you for free and open access by the Theses, Dissertations, and Senior Projects at UND Scholarly Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of UND Scholarly Commons. For more information, please contact [email protected]. SUBSTITUTION AND OXIDATION REACTIONS ON CYCLODIPHOSPH(III)AZANE COMPOUNDS OF THE GROUP 15 ELEMENTS By Joseph T. Musongong Bachelor of Science, University of Dschang, 2003, Master of Science, University of Yaounde I, 2008. A dissertation Submitted to the Graduate School of the University of North Dakota In partial fulfilment of the requirements for the degree of Doctor of Philosophy Grand Forks, North Dakota May 2020 This dissertation, submitted by Joseph T. Musongong in partial fulfilment of the requirements for the Degree of Doctor of Philosophy from the University of North Dakota, has been read by the Faculty Advisory Committee under whom the work has been done, and is hereby approved. Dr. Lothar Stahl Dr. Mark Hoffmann Dr. Harmon Abrahamson Dr. Guodong Du Dr. Edward Kolodka This dissertation is being submitted by the appointed advisory committee as having met all of the requirements of the Graduate School at the University of North Dakota and is hereby approved. Chris Nelson Dean of the Graduate School Date ii PERMISSION Title SUBSTITUTION AND OXIDATION REACTIONS ON CYCLODIPHOSPH(III)AZANE COMPOUNDS OF THE GROUP 15 ELEMENTS Department Chemistry Degree Doctor of Philosophy In presenting this dissertation in partial fulfilment of the requirements for a graduate degree from the University of North Dakota, I agree that the library of this university shall make it freely available for inspection. I further agree that permission for extensive copying for scholarly purposes may be granted by the professor who supervised my dissertation work or, in his absence, by the chairperson of the department or the dean of the Graduate School. It is understood that any copying or publication or other use of this dissertation or part thereof for financial gain shall not be allowed without my written permission. It is also understood that due recognition shall be given to me and to the University of North Dakota in any scholarly use which maybe made of any material in my dissertation. iii TABLE OF CONTENTS TABLE OF CONTENTS .................................................................................................................. iv TABLE OF FIGURES ..................................................................................................................... xii LIST OF TABLES .......................................................................................................................... xvi LIST OF SCHEMES....................................................................................................................... xix LIST OF SYMBOLS AND ABBREVIATIONS ........................................................................... xxi ACKNOWLEDGEMENTS ........................................................................................................... xxv ABSTRACT .................................................................................................................................. xxvi CHAPTER I GENERAL INTRODUCTION .......................................................................................................... 1 1. BACKGROUND TO CYCLODIPHOPHAZANES .............................................................. 1 2. LITERATURE REVIEW ....................................................................................................... 4 2.1 Syntheses of Bis(amino)cyclodiphosph(III)azanes ..................................................... 4 2.2 Synthesis of Bis(amino)cyclodiphosph(V)azane ........................................................ 7 2.3 Synthetic Methods for Metal Complexes of Bis(amino)cyclodiphosph(V)azanes ..... 9 2.4 Application of Cyclodiphosphazanes ...................................................................... 11 2.5 Cyclodiphosph(III/V)azanes as Versatile Ligands .................................................. 14 3. Scope of Dissertation ........................................................................................................... 17 iv CHAPTER II SUBSTITUTION REACTIONS ON CYCLODIPHOSPH(III)AZANE COMPOUNDS OF GROUP 15 ....................................................................................................................................... 18 1. INTRODUCTION ................................................................................................................ 18 2. EXPERIMENTAL ................................................................................................................ 22 General Procedures .......................................................................................................... 22 Description of Instrumentation ........................................................................................ 22 X-ray Crystallography ..................................................................................................... 23 3. SYNTHESES OF COMPOUNDS ........................................................................................ 24 t t {[( BuNP)2( BuN)2]AsPh} 2b .......................................................................................... 24 t t {[( BuNP)2( BuN)2]BiPh} 4b .......................................................................................... 24 t t {[( BuNP)2( BuN)2]AsN3} 2c .......................................................................................... 25 t t {[( BuNP)2( BuN)2]AsN(SiMe3)2} 2d ............................................................................. 26 t t {[( BuNP)2( BuN)2]BiN(SiMe3)2} 4d .............................................................................. 26 t t t {[( BuNP)2( BuN)2]AsO Bu} 2e ...................................................................................... 27 t t {[( BuNP)2( BuN)2]AsOPh} 2f ........................................................................................ 27 t t {[( BuNP)2( BuN)2]SbOSO2CF3} 3g ............................................................................... 28 t t {[( BuNP)2( BuN)2]PI} 1h ............................................................................................... 29 t t {[( BuNP)2( BuN)2]AsI} 2h ............................................................................................. 29 t t {[( BuNP)2( BuN)2]SbI} 3h ............................................................................................. 30 v 4 RESULTS AND DISCUSSIONS ......................................................................................... 30 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]AsPh} 2b ........................ 30 t t Solid-state Structure of {[( BuNP)2( BuN)2]AsPh} 2b .................................................... 33 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]BiPh} 4b ......................... 37 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]AsN3} 2c ........................ 38 t t Solid-state Structure of {[( BuNP)2( BuN)2]AsN3} 2c .................................................... 39 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]AsN(SiMe3)2} 2d ........... 44 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]BiN(SiMe3)2} 4d ............ 46 t t Solid-state Structure of {[( BuNP)2( BuN)2]BiN(SiMe3)2} 4d ........................................ 47 t t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]AsO Bu} 2e .................... 51 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]AsOPh} 2f ...................... 53 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]SbOSO2CF3} 3g ............. 54 t t Solid-state Structure of {[( BuNP)2( BuN)2]SbOSO2CF3} 3g ......................................... 56 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]PI} 1h ............................. 60 t t Solid-state Structure of {[( BuNP)2( BuN)2]PI} 1h ......................................................... 62 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]AsI} 2h ........................... 67 t t Solid-state Structure of {[( BuNP)2( BuN)2]AsI} 2h ....................................................... 67 t t Synthesis and Spectroscopic Analysis of {[( BuNP)2( BuN)2]SbI} 3h ........................... 70 t t Solid-state Structure of {[( BuNP)2( BuN)2]SbI} 3h ....................................................... 71 5. SUMMARY AND CONCLUSIONS ................................................................................... 75 vi CHAPTER III OXIDATION REACTIONS OF CYCLODIPHOSPH(III)AZANE COMPOUNDS OF THE GROUP 15 ELEMENTS ................................................................................................................. 76 1. INTRODUCTION ...............................................................................................................