对二化 () 复合物的综合实验和计算研究
Clément Mazet1, Sebastian P Smidt, Markus Meuwly
1Departments of Organic Chemistry, St. Johanns Ring 19, and Physical Chemistry, Klingelbergstrasse 80, Basel University, CH-4056 Basel, Switzerland.
Journal of the American Chemical Society
|October 28, 2004
概括
化的氧化 (phosphinooxazoline iridium) 复合物与二反应,形成立体选择性二化物复合物. 连接体结构显著影响异构体的能量和形成,由硬体和电子效应驱动.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 立体化学是一种立体化学.
背景情况:
- 和连体的复合体在不对称合成中至关重要.
- 了解连接体对反应性和立体选择性的影响,是催化剂设计的关键.
研究的目的:
- 为了研究一种与二的性[{PHOX}Ir{COD}]{+}复合物的反应.
- 阐明控制二化物复合体形成的立体化学结果和因素.
主要方法:
- 核磁共振 (NMR) 谱学用于监测反应和分配立体化学.
- 密度函数理论 (DFT) 计算以确定异构体的结构和能量.
主要成果:
- 最初形成单个二化物异构体,随后在进一步反应时形成异构体.
- 核磁共振数据允许对三种化物复合物的立体化学赋值.
- DFT计算揭示了立体异构体之间的显著能量差异,突出显示了连接体的影响.
结论:
- 合性酸诺素连接体强烈影响二化物复合物的立体选择性形成.
- 和电子因素的PHOX配体决定化物添加,有利于一个跨-Ir-N配置.
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