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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Synthesis and characterization of binucleating bis(amidinate) ligands and their dialuminum complexes
Bronya Clare1, Niladri Sarker, Richard Shoemaker
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
Abstract:
Two general routes to binucleating bis(amidinate) ligands based on dibenzofuran and 9,9-dimethylxanthene backbones are reported. The free-base form of one of the ligands, (Ph,Mes)L(DBF)H(2), forms a 1:1 adduct with acetone. Single-crystal X-ray diffraction of this adduct reveals bidentate H-bonding of the bis(amidine) to the ketone oxygen. Bond lengths suggest that the individual H-bonds are relatively weak, yet IR spectroscopy shows a significant -26 cm(-1) shift for the carbonyl stretch relative to free acetone. Additionally, the new dialuminum complexes (i)(Pr)L(DBF)Al(2)Me(4) (3), (i)(Pr)L(Xan)Al(2)Me(4) (4), (t)(Bu,Et)L(DBF)Al(2)Me(4) (5), and (t)(Bu,Et)L(Xan)Al(2)Me(4) (6) are prepared by reaction of Al(2)Me(6) with the bis(amidines) in toluene solution. (1)H NMR spectroscopic studies indicate that 3 and 4 interact weakly with certain Lewis bases (DMSO, DMF, pyridine) to effect the exchange of the Al-bound Me groups. Other bases, such as THF and TMEDA, fail to interact. Solid-state structures for 3 and 4 are reported.
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