Light-driven syntheses of monophosphorus compounds

This thesis primarily reports on the synthesis of valuable organic phosphorus compounds (OPCs) such as phosphines and phosphonium salts. Chapter 1 reviews the industrial state-of-the-art procedure to transform P4 into monophosphorus compounds and recently reported developments in the organofunctionalization of inorganic phosphorus compounds are presented. Chapter 2 describes the photochemical synthesis of OPCs such as arylated phosphines and phosphonium salts directly from P4, using carbon-centered radicals provided by reduction of chlorobenzene in presence of super-photoreductant tetrakis(dimethylamino)ethylene (TDAE) with UV-light irradiation. In chapter 3 a simple photocatalytic method for the stannylation of P4 using a cheap, commercially-available distannane (Bu3Sn)2 and anthraquinone as a simple photocatalyst is described. Subsequent ‘one-pot’ transformation of the resulting stannylated monophosphine intermediate (Bu3Sn)3P provides direct access to valuable OPCs. The photoelectrocatalytic arylation of diphenylphosphine (PPh2H) into phosphines and phosphonium salts via reductive activation of organic halides by electrochemically mediated photoredox catalysts (e-PRCat) is reported in chapter 4. Chapter 5 covers a distinct project and describes the synthesis and characterization of bidentate isonitrile iron complexes. Finally, chapter 6 gives a summary of the results described in this thesis and provides a short outlook