Department of Chemistry, University of California, Irvine, California 92697-2025, USA. wevans@ to be a reliable route touci.edu
Inorg Chem. 2010 Jan 4;49(1):222-8. doi: 10.1021/ic901790t.
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(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.
1,3,4,6,7,8-六氢-2H-嘧啶并[1,2-a]嘧啶配体（hpp）-在铀化学中的应用已经通过合成茂金属配合物并研究其反应性进行了探究。(C(5)Me(5))(2)UMe(2)与 1 当量的 Hhpp 反应生成（C(5)Me(5))(2)(hpp)UMe，1，其不再与 Hhpp 进一步反应。(C(5)Me(5))(2)UCl(2)与 Khpp 反应生成（C(5)Me(5))(2)(hpp)UCl，2，其也不与额外的 Khpp 反应。配合物 2 与 NaN(3)反应生成叠氮化物配合物（C(5)Me(5))(2)(hpp)UN(3)，3。三价铀（hpp）-茂金属配合物（C(5)Me(5))(2)(hpp)U 可以通过反应[(C(5)Me(5))(2)U][BPh(4)]与 Khpp 和 2 与 KC(8)合成。配合物 4 可以用 Ph(3)P 水平线Se 氧化生成四价产物(C(5)Me(5))(2)(hpp)U(mu-Se)，5。4 与 Me(3)SiN(3)的反应提供了五价铀配合物（C(5)Me(5))(2)(hpp)U(=NSiMe(3))，6。
