Dyker, C. Adam.2014-10-2120072007AAINR27204http://hdl.handle.net/10222/54912Catenation, or homoatomic bonding, is a principle feature in defining the chemistry of phosphorus. As such, studies directed towards developing new catena-phosphorus chemistry are of fundamental value. Although much is known about neutral and anionic catena-phosphorus compounds, only a limited number of cationic species have been prepared to date.New synthetic methods have now been developed for the preparation of triflate salts of a number of new catena-phosphorus cations consisting of phosphine and phosphonium units. The isolation and characterization of the first monocyclic tri-, tetra- and pentaphosphorus monocations has been achieved. Some examples of acyclic tri- and tetraphosphorus monocations have also been characterized, and the first cyclic tetraphosphorus 1,2-dication and acyclic tetraphosphorus 1,4-dications are reported. Compounds have been characterized by use of multinuclear NMR, including simulations of their often complex 31P {1H} NMR spectra, and X-ray structures have been obtained in most cases. These findings contribute to a systematic development of this emerging area of fundamental phosphorus chemistry.Thesis (Ph.D.)--Dalhousie University (Canada), 2007.Chemistry, Inorganic.text