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半化,一种稳定电子不和复合物的方法:T形Pd和Pt金属循环的案例
Christophe Werlé1, Corinne Bailly, Lydia Karmazin-Brelot
1Institut de Chimie de Strasbourg, Université de Strasbourg, CNRS , 4 rue Blaise Pascal, F-67000 Strasbourg, France.
Journal of the American Chemical Society
|November 5, 2013
概括
一种新的合成方法使用独特的联体创建稳定的T形 (Pd) 和 (Pt) 复合体. 这些持久的异金属化合物具有空置的协调部位,由库伦比相互作用驱动.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
背景情况:
- 形T的14电子复合体是有价值的合成目标.
- 稳定不和金属中心仍然是有机金属化学的一个挑战.
研究的目的:
- 开发稳定,中性T形14电子 (Pd) 和 (Pt) 复合物的合理合成.
- 为了探索三碳 (6-) 烯离子作为半化联体的实用性.
主要方法:
- 通过离子与Pd和Pt金属循环的反应合成异金属复合物.
- 八个新型综合体的结构特征.
- 使用密度函数理论 (DFT) 方法进行理论研究,包括NBO,EDA,ETS-NOCV,AIM和NCI分析.
主要成果:
- 空气稳定和持久的同面异金属复合物的形成.
- 复合体具有 η(1) - 基结合模式,在Pd/Pt中心留下一个空的协调位置.
- 复杂形成的热力学驱动力被确定为Cr(CO) 3部分与空置地点之间的库伦比吸引力.
结论:
- 建立了一个新的合成途径,以稳定T形14电子Pd和Pt复合体.
- 甲基化内基联体有效地稳定不和金属中心.
- DFT计算揭示了这些独特的双金属结构的粘合和热力学稳定性.
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