高电子丰富的零价化合物组10的合成和反应性
Maximilian Dietz1,2, Merle Arrowsmith1,2, Lukas Endres1,2
1Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland 97074, Würzburg, Germany.
Journal of the American Chemical Society
|October 2, 2023
概括
循环 ((氨基) 碳稳定1,4-二形成了新的,和复合物. 这些复合物表现出独特的电子特性和反应性,包括形成仅金属的易斯对和Pt(II) 斯坦尼化物.
科学领域:
- 有机金属化学
- 协调化学
- 材料科学
背景情况:
- 1,4-Diborabenzene (DBB) 是一种具有可调节电子特性的独特连接体.
- 第10组金属 (Ni,Pd,Pt) 在催化和材料科学中至关重要.
- 循环氨基 (CAAC) 是强大的西格玛捐赠体和有效的稳定配体.
研究的目的:
- 通过CAAC-DBB配体稳定新型零价金属组合物的合成和特征.
- 研究这些新的有机金属化合物的电子特性和反应性.
- 探索只有金属的易斯对 (MOLP) 和其它衍生复合物的形成.
主要方法:
- 通过与金属前体反应合成DBB-金属复合物 ([Ni(CO) 4 ,[M(nbe) 2).
- 使用红外光谱学,X射线晶体学和UV-Vis-NIR光谱学进行表征.
- 使用时间依赖密度函数理论 (TD-DFT) 来理解电子过渡和旋转轨道合 (SOC) 的计算研究.
主要成果:
- 分离了[η6-DBB) Ni(CO) (2) 和[η6-DBB) M(nbe) ] (3-M,M=Pd,Pt) 复合物.
- DBB连接体表现出强大的π-捐赠体特性,影响金属中心电子.
- Pd和Pt复合体显示出强烈的近红外吸收,归因于金属中心电子转换.
- 与Fe(CO) 5的反应产生双重CO桥梁M(0) →Fe(0) 的MOLP (4-M).
- Pt复合物经过氧化Sn-H添加,形成Pt(II) 斯坦尼尔化物 (5).
结论:
- CAAC-DBB是稳定10组低价值金属的多功能联体.
- 这些复合物的电子结构决定了它们的光学和反应性质.
- 这项研究证明了新型金属单双和功能化的有机金属复合物的途径.
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