Sengupta Debasish, Bhowmik Koushik, De Goutam, Basu Basudeb
Department of Chemistry, University of North Bengal, Darjeeling 734013, India. ; Tel: +91 353 2776381.
Nano-Structured Materials Division, CSIR-Central Glass & Ceramic Research Institute, 196, Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India. ; Tel: +91 33 23223403.
Beilstein J Org Chem. 2017 Aug 28;13:1796-1806. doi: 10.3762/bjoc.13.174. eCollection 2017.
The present work demonstrates the C-S cross-coupling reaction between aryl halides and thiols using nickel nanoparticles (Ni NPs) supported on reduced graphene oxide (Ni/RGO) as a heterogeneous catalyst. It is observed that the uniformly dispersed Ni NPs supported on RGO could exhibit excellent catalytic activity in C-S cross-coupling reactions and the catalytic application is generalized with diverse coupling partners. Although the electron-rich planar RGO surface helps in stabilizing the agglomeration-free Ni NPs, the catalytic process is found to occur involving Ni(II) species and the recovered catalyst containing both Ni(0)/Ni(II) species is equally efficient in recycle runs. A correlation of loading of Ni species, size of NPs and the intermediate Ni-related heterostructures formed during the catalytic process has been established for the first time, and found to be best in the C-S cross-coupling reaction for Ni(0) and Ni(II) NPs of the average sizes 11-12 nm and 4 nm, respectively.
本工作展示了使用负载在还原氧化石墨烯(Ni/RGO)上的镍纳米颗粒(Ni NPs)作为多相催化剂,实现芳基卤化物与硫醇之间的C-S交叉偶联反应。据观察,负载在RGO上均匀分散的Ni NPs在C-S交叉偶联反应中表现出优异的催化活性,并且该催化应用可推广到多种偶联伙伴。尽管富电子的平面RGO表面有助于稳定无团聚的Ni NPs,但发现催化过程涉及Ni(II)物种,并且回收的同时含有Ni(0)/Ni(II)物种的催化剂在循环运行中同样高效。首次建立了Ni物种负载量、NPs尺寸与催化过程中形成的与Ni相关的中间异质结构之间的相关性,并且发现对于平均尺寸分别为11-12 nm和4 nm的Ni(0)和Ni(II) NPs,在C-S交叉偶联反应中效果最佳。