| Since the first report of an iminophosphine that contained a trivalent, dicoordinate phosphorus atom with a (p-p)pi P=N bond, there have been numerous papers on aminoiminophosphines, N-P=N-. In the past decades, phosphorus compounds containing other low-coordinate multiple bonded elements have received more attention. A wide range of species containing P≡X and P=X bonds is now known.;For many years, the chemistry of PIII species has been limited to the reactivity of the lone pair as a nucleophilic center, e.g., the coordination of transition metal centers by the P lone pair. However, in 1992, the synthesis of a 2-phospha-3-methylbutadiene (1, R = Me) via an "ene" reaction by Angelov and Neilson indicated that the 2-coordinate aminophosphine, (Me3Si)2N-P = NSiMe 3 (III), exhibits nucleophilic character as well. In this project by changing the R group, other 2-phosphabutadienes were synthesized and their derivative chemistry was studied. The compounds underwent a wide variety of reactions without disruption of the butadiene moiety, leading to the formation of novel P-functional derivatives and related compounds.*.;With normal phosphines or phosphoranimines, organolithium compounds are often used as addition or substitution reagents. Either way, the organolithium compound acts as a nucleophilic reagent towards phosphorus. By using different organolithium and quenching reagents to study the reactivity of aminoiminophosphine III, we were able to observe the various electronic and steric effects that influence these reactions.*.;The preparative details of these reactions as well as the structural characterization by multinuclear NMR spectroscopy of several representative products are presented.;*Please refer to dissertation for diagrams. |
