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Molybdenum and iron reaction analogs of nitrogenase
Abstract
In Chapter 1 of this dissertation an introduction to nitrogenase and simple organometallic systems that bind and fix dinitrogen upon protonation is presented. A further elaboration on simple organometallic systems that bind dinitrogen and fix nitrogen is presented in Chapters 2 through 5. Chapter 2 is a review of cis-(bis)dinitrogen molybdenum chemistry. This review is presented to inform the reader how little has been done in the area of cis-(bis)dinitrogen molybdenum chemistry and why the work presented in Chapter 3 using the NP$\sb3$ ligand takes an unusual approach to the formation of a cis-molybdenum dinitrogen compound. The work presented in Chapter 4 is an attempt to substitute vanadium for molybdenum using compounds and procedures similar those presented in Chapter 3. The substitution of vanadium for molybdenum was not successful. The work presented in Chapter 5 is an attempt to employ iron for the preparation of an iron-dinitrogen compound that would produce ammonia upon protonation. The ligand used is the same as in Chapters 3 and 4 but the methods of preparations are very different. This work is more successful, in terms of isolation stability, than those iron-dinitrogen compounds previously reported. The work presented in Chapter 6 is the reaction of starting materials used Chapters 3, 4 and 5 ( ($\rm MoBr\sb3(NP\sb3)\rbrack , \lbrack VCl\sb3(NP\sb3)\rbrack $ and ($\rm FeCl(NP\sb3)\rbrack \lbrack BPh\sb4\rbrack )$ with hydrazine. This was done to explore the reaction between metal compounds and hydrazine in an attempt to produce proposed nitrogen fixation intermediates. Chapter 7 investigates the electrochemical oxidation of cis- and trans-isomers of $\lbrack \rm W(N\sb2)\sb2(PMe\sb2Ph)\sb4\rbrack .$ This work greatly influenced the work presented in Chapter 5 as it demonstrated a possible means of stabilizing dinitrogen-metal compounds. The work in Chapter 8 examines the attempts at producing a zeolite type material from AlVO$\sb4$. This work is very different from that presented in the preceding Chapters in that the physical form of the material was of greater interest than the reactions the material underwent.
Subject Area
Chemistry|Agricultural chemicals
Recommended Citation
Rose, David Jay, "Molybdenum and iron reaction analogs of nitrogenase" (1993). ETD collection for University of Nebraska-Lincoln. AAI9416920.
https://digitalcommons.unl.edu/dissertations/AAI9416920