将素连接的阿米诺波兰与第10组金属的协调
Martine R Tiddens1, Bram T Kappé1, Tom J Smak1
1Organic Chemistry and Catalysis, Faculty of Science, Utrecht University, Institute for Sustainable and Circular Chemistry, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
Chemistry (Weinheim an der Bergstrasse, Germany)
|April 5, 2024
概括
研究人员开发了一种新的配体,用于研究金属复合体中的-双键. 在复合体中观察到侧向协调,揭示了独特的电子相互作用.
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
- 协调化学 协调化学
背景情况:
- 碳-碳双键很容易与过渡金属形成π复合体.
- 类似的π-复合体涉及亚米诺中异电子-双键是罕见的,由于强大的B=N两极化.
研究的目的:
- 为了合成和描述具有-双键的金属复合物.
- 为了研究aminoboranes与10组金属的协调行为.
- 探索B=N π-复合体的电子结构.
主要方法:
- 合成了一种新的二氨基联体 (PhDPBAiPr).
- 与 (Pt), (Pd) 和 (Ni) 复合物的协调研究.
- 进行X射线晶体学以确定分子结构.
- 核磁共振 (NMR) 谱学用于分析结合和电子性质.
主要成果:
- B=N 债券没有协调到 Pt(0) 和 Pd(II) 中心.
- B=N 债券的侧面协调是通过一个Ni(0) 复合体实现的.
- 对Ni(0) 复合物的X射线分析显示了B-N键的延长.
- 协配体选择显著影响了Ni(0) 复合体中的B=N协调,NMR证实了这一点.
- 电子结构分析将Ni-B-N相互作用描述为一个3中心,4电子超键.
结论:
- 这项研究成功地证明了阿米诺B=N双键与Ni(0) 中心的侧向协调.
- 这种协调行为与Pt和Pd复合体不同,并受到协同连接体的影响.
- 这些发现为B=N π-复合物的化学提供了新的见解,扩大了有机金属化学的范围.
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