Knowledge Management System Of Guangzhou Institute of Energy Conversion, CAS
| Kinetic Aspects for the Reduction of CO2 and CS2 with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine | |
Huang, Jing1 ; Chen, Jinzhu1; Gao, Hui1,2; Chen, Limin2
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| 2014-09-15 | |
| Source Publication | INORGANIC CHEMISTRY
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| Volume | 53Issue:18Pages:9570-9580 |
| Abstract | A new water-soluble ruthenium hydride complex [Ru(H)-(bpy)(2)(PTA)]PF6 (bpy = 2,2'-bipyridine, PTA = 1,3,5-triaza-7-phosphaadamantane) (1a) was prepared. 1a reacted with CO2 and CS2 to give the corresponding formate and dithioformate complexes, respectively. Both the insertions of CO2 and CS2 into the Ru-H bond of 1a followed second-order kinetics. The second-order rate constant (k(2)) of CO2 insertion reaction varied from (9.40 +/- 0.41) x 10(-4) M-1 s(-1) in acetone to (1.13 +/- 0.08) x 10(-1) M-1 s(-1) in methanol; moreover, the ln(k(2)) is in good linear relationship with the acceptor number (AN) of the solvent used. Although, the k(2) of CS2 insertion reaction ranged from (3.43 +/- 0.10) M-1 s(-1) in methanol to (24.0 +/- 0.5) M-1 s(-1) in N,N-dimethylformamide, which is 1000 times faster than CO2 insertion. Generally, the k(2) of CS2 insertion increased with the static dielectric constant (D-s) of the reaction medium investigated. For comparison purposes, we further investigated the reactivity of [Ru(H)(bpy)(2)(PPh3)]PF6 (PPh3 = triphenylphosphine) (1b) with CO2 and CS2. 1b reacted with CO2 slowly in the methanol with a k(2) of (1.46 +/- 0.09) x 10(-3) M-1 s(-1), yielding a formate complex [Ru(eta(1)-OC(H)=O)(bpy)(2)(PPh3)]PF6 (2b). The reaction of 1b with CS2 is 1000 times faster than that of CO2. The structures of 1a, 1b, and 2b were determined by X-ray crystallographic analysis. |
| Subtype | Article |
| WOS Headings | Science & Technology ; Physical Sciences |
| DOI | 10.1021/ic500866d |
| WOS Subject Extended | Chemistry |
| WOS Keyword | RHODIUM-CATALYZED HYDROGENATION ; PROTONATED AMINE ARM ; CARBON-DIOXIDE ; FORMIC-ACID ; HOMOGENEOUS HYDROGENATION ; ELECTROCHEMICAL REDUCTION ; AQUA COMPLEXES ; WATER ; REACTIVITY ; DISULFIDE |
| Indexed By | SCI |
| Language | 英语 |
| WOS Subject | Chemistry, Inorganic & Nuclear |
| WOS ID | WOS:000341747900015 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.giec.ac.cn/handle/344007/10603 |
| Collection | 中国科学院广州能源研究所 |
| Affiliation | 1.Chinese Acad Sci, Guangzhou Inst Energy Convers, CAS Key Lab Renewable Energy, Guangzhou 510640, Guangdong, Peoples R China 2.S China Univ Technol, Coll Environm & Energy, Guangdong Prov Key Lab Atmospher Environm & Pollu, Guangzhou 510006, Guangdong, Peoples R China |
| First Author Affilication | GuangZhou Institute of Energy Conversion,Chinese Academy of Sciences |
| Recommended Citation GB/T 7714 | Huang, Jing,Chen, Jinzhu,Gao, Hui,et al. Kinetic Aspects for the Reduction of CO2 and CS2 with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine[J]. INORGANIC CHEMISTRY,2014,53(18):9570-9580. |
| APA | Huang, Jing,Chen, Jinzhu,Gao, Hui,&Chen, Limin.(2014).Kinetic Aspects for the Reduction of CO2 and CS2 with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine.INORGANIC CHEMISTRY,53(18),9570-9580. |
| MLA | Huang, Jing,et al."Kinetic Aspects for the Reduction of CO2 and CS2 with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine".INORGANIC CHEMISTRY 53.18(2014):9570-9580. |
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