在 (dtbbpy) NiII(aryl) ((Br) 中激发状态 Ni-Br 键同解的综合多参考研究
Sanchit Kumar1, Sayan Dutta1, Luigi Cavallo1
1KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
Inorganic chemistry
|October 17, 2024
概括
可见光驱动尼克尔复合体中的Ni-Br键同解,通过金属到联体电荷转移 (MLCT) 激发状态,与Ni-C键断裂不同. 这种机制对于金属光电氧催化非常重要.
科学领域:
- 有机金属化学 有机金属化学
- 摄影化学的使用.
- 催化剂是一种催化剂.
背景情况:
- 在金属光电氧催化过程中,可见光驱动的Ni-C(aryl) 键同解是众所周知的.
- 在这些系统中对Ni-化物键同解的理论见解有限.
研究的目的:
- 阐明 (dtbbpy) NiII() 复合体中光诱导的 Ni-Br 键破裂的机制.
- 为了解尼化键同解引入一种新的电子结构框架.
主要方法:
- 采用了多重引用的初始计算.
- 激发状态潜在能量表面的特征,用于金属到质电荷转移 (MLCT) 和质到金属电荷转移 (LMCT).
主要成果:
- 光诱导的Ni-Br解离通过Ni (II) 开始到MLCT兴奋状态.
- 系统间穿越到排斥三重体状态 (MLCT和LMCT) 便于通过德克斯特能量转移打破Ni-Br键.
- 光催化剂的存在促进了Ni-Br同解,而其缺乏则有利于Ni-C(aryl) 同解.
- 氧化后的Ni (III) 种对Ni-Br或Ni-C (aryl) 键的激活没有反应.
结论:
- 提出了可见光驱动的Ni-Br键同解的详细机制.
- 电子结构和兴奋状态决定了复合体中键裂解的模式.
- 了解这些机制是优化光催化交叉合反应的关键.
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