Organohydrazido(2-) complexes of tungsten and molybdenum. Potential inorganic model complexes for the nitrogen-nitrogen bond cleavage step in nitrogen fixation

Chapter one contains a brief overview of nitrogen fixation. An opinion of the recent crystal structure of nitrogenase, a survey of inorganic model compounds, and a summary of the reactivity of bound dinitrogen are included. Emphasis is given to chemistry relevant to hydrazido(2-) and organohydrazido(2-) complexes of tungsten and molybdenum. Chapter two contains the experimental methods and synthetic procedures for all complexes made during this research along with the physical data for all new complexes. Chapter three presents the results and discussion of the synthesis and reactivity of new organohydrazido(2-) complexes of tungsten and molybdenum. These new complexes were subjected to exhaustive protonation and proved to be reaction analogs of unsubstituted hydrazido(2-) complexes. Attempts were made to react these new complexes with stoichiometric amounts of acid to isolate new intermediates past the hydrazido(2-) stage. In the discussion an attempt is made to explain the anomalous reactivity of $\rm\lbrack WCl\sb2(NNPh\sb2)(PMe\sb2Ph)\sb3\rbrack$ with water. Chapter four discusses the results of work on cis- and trans-$\rm\lbrack W(N\sb2)\sb2(PMe\sb2Ph)\sb4\rbrack .$ Results of alkylation and acylation reactions are presented. The effect of dinitrogen pressure on the product distribution of cis and trans isomers during synthesis of these isomers is discussed. Chapter five presents a short overview of hydrothermal, and Sol-Gel synthetic techniques. Results are given of attempts to use these techniques to synthesize open framework complexes of the formula AlVO$\sb4.$ The Appendices give $\rm\sp{31}P\{\sp1H\}$ and $\sp1$H NMR spectra of many of the compounds synthesized, as well as the crystal structure data for $\rm\lbrack WCl\sb2(NNPh\sb2)(PMe\sb2Ph)\sb3\rbrack ,\ \lbrack WCl\sb2(NNMe\sb2)(PMe\sb2Ph)\sb3\rbrack ,$ and $\rm\lbrack Fe(CO)\sb3(\eta\sp5$-$\rm (C\sb6H\sb6OCH\sb3)\rbrack\lbrack BF\sb4\rbrack .$ Also included are copies of a note and communication resulting from this work