The photochemical reactions of trifluorophosphine iron (0) carbonyl species: Olefin and cluster chemistry.

摘要

Gas phase photochemical reactions were performed with trifluorophosphine iron (0) carbonyl species and the olefins, tetrafluoroethylene and ethylene. It was observed that these two olefins behave very differently from each other. The ethylene olefin tends to prefer substitution type reactions while the tetrafluoroethylene olefin prefers scrambling type reactions. It was also observed that the substituted products resulting from these two olefins are very different. Infrared data show that in the hydrocarbon olefin system the presence of isomers exists, while in the fluorinated olefin system there is only the evidence for one preferred isomer. This olefin work led to competition reactions to study the rate of addition of the previous two olefins and the two ligands, CO and PF3.;From the olefin work two side projects arose; the study of any cluster chemistry as well as minor species forming from the tetrafluoroethylene olefin. From this work a green volatile iron cluster of the composition Fe3(PF 3)x(CO)12-x was proposed formed from the irradiation of a Fe(PF3)x(CO)5-x. Formation of minor species from the tetrafluoroethylene olefin were confirmed as being C 3F6Fe(PF3)x(CO)4-x and C 4F8Fe(PF3)x(CO)4-x species. These species were characterized as having an octahedral geometry and are considered to be stereochemically rigid.;The olefin system, particularly the fluorinated olefin system, is more complicated than previously imagined. This dissertation has answered many questions about the olefin substituted trifluorophosphine iron (0) carbonyl system. It has also opened the door to many unanswered questions as good research tends to do. Data will be presented and discussed in the following pages which has led to the above conclusions.