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Nadezhda Sevostyanova Sergey Batashev Ilya Nifant'ev Alexander Vinogradov Alexander Tavtorkin 《国际化学动力学杂志》2019,51(4):274-279
Operating over the entire length from the region of initial rates to deep conversions of cyclohexene, hydromethoxycarbonylation kinetic models have been obtained in the temperature range of 358–378 K. At 378 K, a conclusion on a higher stability of the diphosphine complex [HPd(TBDPN)(CH3OH)]OTs compared to [HPd(CO)2OTs] under hydromethoxycarbonylation conditions has been made based on the comparison of the kinetic model constant values. 相似文献
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Jinbo Zhao Dr. Peng Wu Enyi Lai Dr. Jiancheng Li Yilin Chen Wenjun Jiang Prof. Dr. Binju Wang Prof. Dr. Hongping Zhu 《化学:亚洲杂志》2021,16(21):3453-3461
Reactions of N,P-Ligands as Ph2P(o-NMe2C6H4) (1L), 2,6-iPr2C6H3NHC(Ph)=NC6H4(o-PPh2) (2L), and Ph2PN(R)PPh2 (R=iPr (3L), cyclo-C6H11 (4L), tBu (5L), CH2C4H7O (6L)) each with dicobalt octacarbonyl produced complexes [1LCo(CO)3]2 ( 1 ), [2LCo(CO)(μ-CO)2Co(CO)3] ( 2 ), [3LCo(CO)3]+[Co(CO)4]− ( 3 ), [3LCo(CO)2]2 ( 4 ), [4LCo(CO)2]2 ( 5 ), [5LCo(CO)2]+[Co(CO)4]− ( 6 ), and [6LCo(CO)2]+[Co(CO)4]− ( 7 ). Complexes 1–7 have all been structurally characterized by X-ray crystallography, IR and NMR spectroscopies, and elemental analysis. Catalytic tests on transformation of ethylene oxide (EO), CO and MeOH into methyl 3-hydroxypropionate (3-HMP) indicate that complexes 1 – 7 are active, where ion-pair complexes 3 and 6 – 7 behave more excellently (by achieving 88.4–93.6% 3-HMP yields) than the neutral species 1 – 2 and 4 – 5 (35.0–46.5% 3-HMP yields) when the reactions are all operated at 2 MPa CO pressure and 50 °C in MeOH solvent. Density functional theory (DFT) study by selecting 3 as a model suggests a cooperative catalytic reaction mechanism by [Co(CO)4]− and its counter cation [3LCo(CO)3]+. The cobalt-homonuclear ion-pair catalyzed hydroalkoxycarbonylation of EO is present herein. 相似文献
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