Thioxobimanes: Structural and Chelating Studies
2Department of Chemical Research Support, Weizmann Institute of Science, Rehovot
3Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva
4Department of Chemical Engineering and Biotechnology, Ariel University, Ariel
syn-(Me,Me)Bimane (1) bears the heterocyclic molecular core of a well-known class of biologically relevant fluorescent dyes. Despite their intrinsic characteristics as chelating agents (O-donors and sterically available π system) the coordination chemistry of bimanes has not been explored. Recently, we reported the first example of a cationic Pd(II) complex containing syn-(Me,Me)bimane as an O-donor chelating ligand.[1]
In order to expand the scope of bimanes by accessing derivatives with different chelating and fluorescence properties while keeping the low number of atoms in their basic structure, we reasoned that the carbonyl oxygen atoms could be replaced by sulfur ones. We applied traditional thionating chemistry (Lawesson’s reagent and P4S10) in the preparation of syn-monothioxobimane (2), syn-dithioxobimane (3) and anti-dithioxobimane (4). Our preliminary results indicate that the introduction of sulfur atoms to the bimane core results in significant depression of the original fluorescence intensity, in the UV-vis region.
X-ray data and computational quantum mechanical modeling methods were used to shed light on the topology and dynamics of the bimane core structure. Our latest results describing syn-thioxobimanes as ligands in metal complexes as well as their structural and spectroscopic implications will be presented.
[1] Das, P. J.; Diskin-Posner, Y.; Firer, M.; Montag, M.; Grynszpan, F., Dalton Trans. 2016, 45, 17123-17131.
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