Stable Discrete Pt-1(0) in Crown Ether with Ultra-High Hydrosilylation Activity
文献类型：期刊论文
| 作者 | Liu, Kairui1; Shen, Xing1,2; Bai, Shi3; Zhang, Z. Conrad1 |
| 刊名 | CHEMCATCHEM
 |
| 出版日期 | 2019-11-26 |
| 页码 | 7 |
| 关键词 | Crown Ether Density Functional Calculations Hydrosilylation Metal Atom Catalyst Platinum |
| ISSN号 | 1867-3880 |
| DOI | 10.1002/cctc.201901577 |
| 英文摘要 | Obtaining reduced discrete metal atoms that are stable in liquid solvents by in-situ reduction of an ionic metal precursor has been a challenge until recently. A liquid surfactant polydimethylsiloxane-polyethylene glycol (PDMS-PEG) enabled the synthesis of stable discrete platinum atoms (Pt-1) by reducing Pt(IV) and Pt(II) salts. Here we report the successful preparation of discrete mononuclear platinum atoms (Pt-1) in a crown ether, [15]crown-5, as a structurally much simpler solvent, and the prepared Pt-1@[15]crown-5 was demonstrated for ultra-high catalytic activity and selectivity in hydrosilylation reactions. A combination of spectroscopic characterizations proves the reduced Pt species is Pt-1(0) with partially positive charge. Pt-195 NMR and DFT calculation indicate the Pt-1(0) is stabilized by the pseudo octahedral structure of ([15]crown-5)PtCl2-H2+ involving two adjacent oxygens from the crown ether ring, although the oxygens in the crown ether ring have been known to host and stabilize certain metal cations. The Pt-1@[15]crown-5 shows ultrahigh activity (TOF of 8.3x10(8) h(-1)) with excellent terminal adducts selectivity in catalytic olefin hydrosilylation. This catalyst was found to be highly stable under hydrosilylation conditions. For examples, the turnover number (TON) exceeded 1.0x10(9) for hydrosilylation between 1-octene and (Me3SiO)(2)MeSiH without showing sign of deactivation; the TON exceeded 2.0x10(8) while the catalyst remained active for a catalytically more demanding reaction between styrene and (Me3SiO)(2)MeSiH. |
| WOS关键词 | CATALYTIC HYDROSILYLATION ; PLATINUM(0)-CARBENE COMPLEXES ; COORDINATION CHEMISTRY ; PLATINUM ; NANOPARTICLES ; EFFICIENT ; NMR ; OXIDATION ; SIZE |
| 资助项目 | "Global Expert" program of China ; State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences ; National Institute of General Medical Sciences-NIGMS from the National Institutes of Health[5 P30 GM110758-02] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000498435300001 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 资助机构 | "Global Expert" program of China ; State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences ; National Institute of General Medical Sciences-NIGMS from the National Institutes of Health |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/38379]  |
| 专题 | 中国科学院过程工程研究所 |
| 通讯作者 | Bai, Shi; Zhang, Z. Conrad |
| 作者单位 | 1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, State Key Lab Catalysis, Dalian 116023, Peoples R China 2.Chinese Acad Sci, Inst Proc Engn, Beijing 100049, Peoples R China 3.Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA |
| 推荐引用方式 GB/T 7714 | Liu, Kairui,Shen, Xing,Bai, Shi,et al. Stable Discrete Pt-1(0) in Crown Ether with Ultra-High Hydrosilylation Activity[J]. CHEMCATCHEM,2019:7. |
| APA | Liu, Kairui,Shen, Xing,Bai, Shi,&Zhang, Z. Conrad.(2019).Stable Discrete Pt-1(0) in Crown Ether with Ultra-High Hydrosilylation Activity.CHEMCATCHEM,7. |
| MLA | Liu, Kairui,et al."Stable Discrete Pt-1(0) in Crown Ether with Ultra-High Hydrosilylation Activity".CHEMCATCHEM (2019):7. |
入库方式： OAI收割
来源：过程工程研究所
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