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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
Uranium metallocene complexes of the 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato ligand, (hpp)(-)
William J Evans1, Elizabeth Montalvo, Joseph W Ziller
1Department of Chemistry, University of California, Irvine, California 92697-2025, USA. wevans@ to be a reliable route touci.edu
Abstract:
The utility of the 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato ligand, (hpp)(-), in uranium chemistry has been probed by synthesizing metallocene complexes and studying their reactivity. (C(5)Me(5))(2)UMe(2) reacts with 1 equiv of Hhpp to form (C(5)Me(5))(2)(hpp)UMe, 1, which does not react further with Hhpp. (C(5)Me(5))(2)UCl(2) reacts with Khpp to form (C(5)Me(5))(2)(hpp)UCl, 2, which similarly does not react with additional Khpp. Complex 2 reacts with NaN(3) to form the azide complex, (C(5)Me(5))(2)(hpp)UN(3), 3. The trivalent uranium (hpp)(-) metallocene complex, (C(5)Me(5))(2)(hpp)U, 4, can be synthesized by the reaction of [(C(5)Me(5))(2)U][BPh(4)] with Khpp and from 2 with KC(8). Complex 4 can be oxidized with Ph(3)P horizontal lineSe to produce the tetravalent product, [(C(5)Me(5))(2)(hpp)U](2)(mu-Se), 5. The reaction of 4 with Me(3)SiN(3) provides the pentavalent uranium complex, (C(5)Me(5))(2)(hpp)U(=NSiMe(3)), 6.
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