Synthesis of Novel Phosphinine Coordination Compounds and their Reactivity toward small Molecules

This doctoral thesis reports on the synthesis and characterization of novel phosphinine coordination compounds and their reactivity toward small molecules. Chapter 1 gives a general overview of phosphinine chemistry, discussing their rich coordination chemistry and application in catalysis. Chapter 2 reports on the selective halogenation of an anionic phosphinine iron(0) complex, which led to the formation of rare halogenated phosphacyclohexadienyl complexes. Chapter 3 shows the reactivity of a phospha-bora-norbornadiene with nitriles and alkynes. The results show phosphinine derivatives incorporating a Lewis acidic site can possess frustrated Lewis pair (FLP) type reactivity. In Chapter 4, the synthesis of pyridyl-phosphinine-based phosphinoborates is discussed. Chapter 5 reports on the facile splitting of carbon dioxide by an anionic pyridyl-phosphinine iron(0) complex. Chapter 6 addresses the synthesis on a homoleptic pyridyl-phosphinine nickel(0) complex which is capable of splitting carbon-halide bonds. Finally, Chapter 7 summarizes all results of this thesis followed by a brief outlook on the future of phosphinine chemistry.