Cobalt Carbonyls Stabilized by N, P‐Ligands: Synthesis, Structure, and Catalytic Property for Ethylene Oxide Hydroalkoxycarbonylation. Issue 21 (14th September 2021)

• Record Type: Journal Article
• Authors: Zhao, Jinbo; Wu, Peng; Lai, Enyi; Li, Jiancheng; Chen, Yilin; Jiang, Wenjun; Wang, Binju; Zhu, Hongping
• Is Part Of: Chemistry, an Asian journal. Volume 16:Issue 21(2021)
• Page Start: 3453
• Page End: 3461
• Publication Date: 2021-09-14
• Subjects: crystal structures -- ethylene oxide -- hydromethoxycarbonylation -- homogeneous catalysis -- homonuclear ion pair; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.202100688
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: Reactions of N, P‐Ligands as Ph2 P( o ‐NMe2 C6 H4 ) ( 1 L), 2, 6‐ i Pr2 C6 H3 NHC(Ph)=NC6 H4 ( o ‐PPh2 ) ( 2 L), and Ph2 PN(R)PPh2 (R= i Pr ( 3 L), cyclo ‐C6 H11 ( 4 L), t Bu ( 5 L), CH2 C4 H7 O ( 6 L)) each with dicobalt octacarbonyl produced complexes [ 1 LCo(CO)3 ]2 (1 ), [ 2 LCo(CO)( μ ‐CO)2 Co(CO)3 ] (2 ), [ 3 LCo(CO)3 ] + [Co(CO)4 ] − (3 ), [ 3 LCo(CO)2 ]2 (4 ), [ 4 LCo(CO)2 ]2 (5 ), [ 5 LCo(CO)2 ] + [Co(CO)4 ] − (6 ), and [ 6 LCo(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 [ 3 LCo(CO)3 ] + . The cobalt‐homonuclear ion‐pair catalyzed hydroalkoxycarbonylation of EO is present herein. Abstract : [ 3 LCo(CO)3 ] + [Co(CO)4 ] − (3) catalyzes the ethylene oxide hydromethoxycarbonylation into 3‐HMP, exhibiting the cobalt‐homonuclear ion‐pair catalysis mode.