کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1323656 | 1499871 | 2014 | 6 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: DFT study of the single electron transfer mechanisms in Ni-Catalyzed reductive cross-coupling of aryl bromide and alkyl bromide DFT study of the single electron transfer mechanisms in Ni-Catalyzed reductive cross-coupling of aryl bromide and alkyl bromide](/preview/png/1323656.png)
• We investigated mechanisms of the Ni-catalyzed reductive cross-coupling of aryl bromide and secondary alkyl bromide.
• Two single electron transfer mechanisms are feasible.
• The rate-limiting step is the radical addition step with the energy barrier of 10.42 kcal/mol.
• We studied four possible single electron transfer mechanisms and two concerted mechanisms.
Ni-catalyzed reductive cross-coupling reactions of electrophilic regents provide an important method to form C–C bonds. The present study explored several single electron transfer mechanisms for Ni-catalyzed reductive cross-coupling of aryl bromide and secondary alkyl bromide using Density Functional Theory (DFT) calculations. The results showed that two of the proposed mechanisms were feasible. One was a six-step catalytic cycle including oxidative addition, reduction, radical production, radical addition, reductive elimination and catalyst regeneration. The other was a five-step mechanism involving radical production, reduction, oxidative addition, radical addition, and reductive elimination. The rate-limiting step for both mechanisms was the radical addition step with the energy barrier of 10.42 kcal/mol. All DFT calculations were implemented in the gas phase.
Four of the proposed single electron transfer mechanisms in Ni-catalyzed reductive cross-coupling of aryl bromide and secondary alkyl bromide were studied using DFT calculations. The results showed that two of them were feasible in which the rate-limiting step was the radical addition step with the energy barrier of 10.42 kcal/mol.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 770, 1 November 2014, Pages 130–135