一个Rh-Mo-Rh二硫酸复合体的两电子减少,以形成三重基态,与CO协调模式的变化相关
Satoshi Muratsugu1, Keitaro Sodeyama, Fusao Kitamura
1Department of Chemistry, School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-Ku, Tokyo, 113-0033, Japan.
Journal of the American Chemical Society
|January 14, 2009
概括
研究人员合成了一种新型异构金属三核复合体,表现出可逆的两电子还原. 这种氧化还原过程涉及结构和旋转状态的变化,为金属乙烯化学提供了洞察力.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
- 材料科学 材料科学 材料科学
背景情况:
- 多核金属复合体具有独特的电子和结构性质.
- 金属二甲基乙烯复合物因其氧化还原活性而引起人们的兴趣.
研究的目的:
- 为了合成和描述一个新的dithiolato-bridged异构金属三核复合体.
- 为了研究氧化还原行为和相关的结构/旋转状态变化.
主要方法:
- 不同金属三核复合物的合成.
- 电化学研究以确定氧化还原潜力.
- 密度函数理论 (DFT) 计算用于结构和电子分析.
主要成果:
- 合成了一种dithiolato桥接的异构金属三核复合体,[{(eta(5) -C(5) Me(5)) Rh(S(2) C(6) H(4)) }(2) Mo(CO) }(2) ] (1),被合成.
- 综合体1显示可逆的一步两电子减少与潜在的反转.
- 氧化还原过程涉及CO协调和自旋状态 (Rh(III) -Mo(0) -Rh(III) 到Rh(II) -Mo(0) -Rh(II)) 的可逆变化.
结论:
- 这项研究提供了多核金属乙烯复合物的第一个例子,具有可逆的多电子还氧化过程.
- 观察到的氧化还原诱导的结构和旋转状态变化被DFT计算证实.
- 这项工作为设计具有可调节电子属性的复合体提供了基础.
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