HCl and O-2 co-activated bis(8-quinolinolato) oxovanadium(IV) complexes as efficient photoactive species for visible light-driven oxidation of cyclohexane to KA oil
HCl and O-2 co-activated bis(8-quinolinolato) oxovanadium(IV) complexes as efficient photoactive species for visible light-driven oxidation of cyclohexane to KA oil
复制标题
HCl 和 O-2 共激活双（8-羟基喹啉）氧钒（IV）配合物作为有效的光活性物质，用于可见光驱动的环己烷氧化成 KA 油
DOI：
10.1039/c8cy01241e
复制
发表时间：
2019
影响因子：
5
通讯作者：
Yin Dulin
中科院分区：
文献类型：
--
作者：
She Jialuo;Lin Xiangfeng;Fu Zaihui;Li Jianwei;Tang Senpei;Lei Ming;Zhang Xin;Zhang Chao;Yin Dulin
本文报道了三种双（8-羟基喹啉）氧钒（IV）配合物，它们在氧气（1 atm）下，在乙腈中，HCl参与下，对可见光诱导的环己烷氧化具有活性，获得了大于18%的转化率和86%的KA油（环己酮和环己醇）选择性，沿着有少量氯化产物。值得注意的是，这些VIVOQ 2复合物不仅在光催化活性方面基本上与VIVO（acac）2和一些典型VV-化合物相当，而且对KA油具有更高的选择性。光谱表征（XPS，FT-IR和UV-vis）和密度泛函理论计算支持VIVOQ 2配合物可以被HCl和O2共活化，形成含VVO（OH）的光活性（PA）物种，其中一个侧配体的苯氧基自由基和一个轴向配位的氯，这是负责本光催化氧化。值得注意的是，增加VIVOQ 2络合物的Cl-取代基，特别是反应体系中水的量明显减缓了此类PA物种的生成，这显著提高了KA油的选择性。
This paper reports three bis(8-quinolinolato) oxovanadium(IV) complexes that are active for visible light-induced cyclohexane oxygenation under O2 (1 atm) in acetonitrile with HCl participation, achieving greater than 18% conversion and 86% selectivity for KA oil (cyclohexanone and cyclohexanol), along with a small amount of chlorinated product. Notably, these VIVOQ2 complexes are not only basically comparable to VIVO(acac)2 and some typical VV-compounds in photocatalytic activity but are also more selective for KA oil. Spectral characterizations (XPS, FT-IR and UV-vis) and DFT calculations support that VIVOQ2 complexes can be co-activated by HCl and O2 to form the VVO(OH)-containing photoactive (PA) species with one pendant ligand's phenoxyl radical and an axially coordinated chlorine, which are responsible for the present photocatalytic oxidation. Noteworthily, increasing the Cl-substituents of VIVOQ2 complexes and especially the amount of water in the reaction system obviously decelerated the generation of such PA species, which significantly improved the selectivity for KA oil.