University of Windsor
Scholarship at UWindsor
UWill Discover Undergraduate Conference
UWill Discover 2017
Mar 31st, 10:30 AM - 11:50 AM
The Oxidation Chemistry of Low Valent
Phosphorus
Maxemilian C. Nascimento
University of Windsor, [email protected]
Follow this and additional works at: http://scholar.uwindsor.ca/uwilldiscover
Nascimento, Maxemilian C., "The Oxidation Chemistry of Low Valent Phosphorus" (2017). UWill Discover Undergraduate Conference.
5.
http://scholar.uwindsor.ca/uwilldiscover/2017/session4/5
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Abstract: The Oxidation Chemistry of Low Valent Phosphorus
The “main group” of the periodic table refers to elements within the s- and p-block. These
elements display an incredible variety of properties and thus have many uses industrially, such as
components within electronics or in the production of polymers, to name a few.1 Our research
group has been interested in the development of new configurations and bonding motifs for some
main group elements within the p-block.2 Specifically, we are interested in the synthesis of
molecules containing elements in low oxidation states or valence states, which are electron rich
and can undergo a variety of further reactivities and chemistry, such as: transition metal
coordination, insertion chemistry, and oxidation reactions.3 Despite their reactivity and increased
electron density, these molecules require configurations that allow them to be relatively stable so
that they can be easily handled for further chemistry and modification. One of these molecules that
our research group has reported is called a “triphosphenium cation” which refers to a dicoordinate
(low valent) phosphorus atom (in the +1 oxidation state) coordinated and stabilized by a chelating
diphosphine ligand.4 Recently, we have found one of these triphosphenium molecules,
[PIdppe][Br], to be very useful in the generation of other phosphorus molecules containing a low
oxidation state phosphorus centre.5
The focus of my project is exploring new ligands to react with this triphosphenium
molecule to generate new or useful phosphorus-containing molecules. I have been successful in
employing tetrathiocine ligands in oxidative addition reactions, as an alternative and more
convenient method to generate a diphosphane molecule, which had been previously shown to
generate stable radical molecules.6 These investigations were performed using air and moisture
free techniques during the synthesis and characterization of these compounds. Multinuclear
Nuclear Magnetic Resonance (NMR) spectroscopy was used to characterize the compounds as
well as provide mechanistic insight to the reaction. X-ray crystallography was also employed to
identify the bonding and connectivity of these new molecules. Future applications of these results
can include ligands for transition metals, and trithiaphosphite applications for industrial uses such
as lubricants and oils.
1
C. L. B. Macdonald, B. D. Ellis and A. Swidan, in Encyclopedia of Inorganic and
Bioinorganic Chemistry, John Wiley & Sons, Ltd, 2011.
2
B. D. Ellis and C. L. B. Macdonald, Mod. Asp. Main Gr. Chem., 2006, 917, 108–121.
3
B. D. Ellis and C. L. B. Macdonald, Coord. Chem. Rev., 2007, 251, 936–973.
4
E. L. Norton, K. L. S. Szekely, J. W. Dube, P. G. Bomben and C. L. B. Macdonald, Inorg.
Chem., 2008, 47, 1196–1203.
5
S. C. Kosnik, J. F. Binder, M. C. Nascimento and C. L. B. Macdonald, J. Vis. Exp., 2016,
3–9.
6
C. Kirst, B. E. Bode, D. B. Cordes, P. S. Nejman, A. M. Z. Slawin, K. Karaghiosoff and J.
D. Woollins, Dalt. Trans., 2016, 6348–6351.