title: Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation.
abstract: Four perfluoroalkyl cobalt(III) fluoride complexes have been synthesized and characterized by elemental analysis, multinuclear NMR spectroscopy, X-ray crystallography, and powder X-ray diffraction. The remarkable cobalt fluoride (19)F NMR chemical shifts (-716 to -759 ppm) were studied computationally, and the contributing paramagnetic and diamagnetic factors were extracted. Additionally, the complexes were shown to be active in the catalytic fluorination of p-toluoyl chloride. Furthermore, two examples of cobalt(III) bis(perfluoroalkyl)complexes were synthesized and their reactivity studied. Interestingly, abstraction of a fluoride ion from these complexes led to selective formation of cobalt difluorocarbene complexes derived from the trifluoromethyl ligand. These electrophilic difluorocarbenes were shown to undergo insertion into the remaining perfluoroalkyl fragment, demonstrating the elongation of a perfluoroalkyl chain arising from a difluorocarbene insertion on a cobalt metal center. The reactions of both the fluoride and bis(perfluoroalkyl) complexes provide insight into the potential catalytic applications of these model systems to form small fluorinated molecules as well as fluoropolymers.
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Matthew C
authors.initials: MC
authors.lastname: Leclerc
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Julia M
authors.initials: JM
authors.lastname: Bayne
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Graham M
authors.initials: GM
authors.lastname: Lee
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Serge I
authors.initials: SI
authors.lastname: Gorelsky
authors.affiliation: Department of Chemistry, The University of Alabama , Tuscaloosa, Alabama 35487, United States.
authors.forename: Monica
authors.initials: M
authors.lastname: Vasiliu
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Ilia
authors.initials: I
authors.lastname: Korobkov
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Harrison
authors.affiliation: Department of Chemistry, The University of Alabama , Tuscaloosa, Alabama 35487, United States.
authors.forename: David A
authors.initials: DA
authors.lastname: Dixon
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: R Tom
authors.initials: RT
authors.lastname: Baker