帕拉的跨二复合物 (II)
Vladimir V Grushin1, William J Marshall
1Central Research & Development, E. I. DuPont de Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880, USA. vlad.grushin-1@usa.dupont.com
Journal of the American Chemical Society
|January 7, 2009
概括
研究人员合成了新型的二复合物trans-[(Py) 2Pd(F) 2和trans-[(t-BuPy) 2Pd(F) 2 ,它们表现出异常短的-键. 这些发现挑战了现有的关于d(8) 方形复合体中的金属-连接体结合的理论.
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:
- 复合物在催化和材料科学中至关重要.
- 了解金属-键是设计新功能材料的关键.
- 之前的研究还没有完全探索过二d(8) 方形复合体.
研究的目的:
- 合成和表征新的跨二d(8) 方形复合物.
- 研究这些复合物的结合特性和结构性质.
- 探索相关的复合物的热分解路径.
主要方法:
- 从相应的化物和银化物 (AgF) 中合成复合物trans-[(Py) 2Pd(Ph) ((F) ]和trans-[(t-BuPy) 2Pd(F) ].
- 在无水中进行热分解实验.
- 独立合成并对新型二复合物 trans-[(Py) 2Pd(F) 2 和 trans-[(t-BuPy) 2Pd(F) 2 的完整表征.
- 通过X射线晶体学来确定Pd-F键距离.
主要成果:
- 前体复合物的热分解产生了黑,双和新的二复合物.
- 首个跨-二d(8) 方形复合体,即跨-[(Py) 2Pd(F) 2) 和跨-[(t-BuPy) 2Pd(F) 2) 已成功合成和表征.
- 这些复合体表现出前所未有的短Pd-F键距离 (1.947(4)-1.958(4) Å),比前体复合体更短.
- 观察到的Pd-F债券长度与基于d(pi) -p(pi) 排斥的理论预测相矛盾.
结论:
- 这些新型二相复合物的合成扩大了已知的d(8) 方形复合物的家族.
- 短的Pd-F键距离表明强烈的金属-连接体相互作用,并挑战当前的结合模型.
- 需要进一步研究这些复合体中形成和结合的机制.
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