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Effect of PDI ligand binding pattern on the electrocatalytic activity of two Ru(II) complexes for CO 2 reduction
Author(s) -
Shi Ningning,
Xie Wangjing,
Gao Weisong,
Wang Jinmiao,
Zhang Shifu,
Fan Yuhua,
Wang Mei
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5551
Subject(s) - chemistry , acetonitrile , ligand (biochemistry) , tetrahydrofuran , electrochemistry , redox , denticity , medicinal chemistry , pyridine , perchlorate , deprotonation , trigonal bipyramidal molecular geometry , inorganic chemistry , crystallography , stereochemistry , solvent , crystal structure , ion , electrode , organic chemistry , biochemistry , receptor
The electrochemical properties of two complexes, [Ru II (η 3 ‐(N,N,N)‐ OMe PDI)Cl 2 (PPh 3 )] 0 ( 1 ) and [Ru II (η 2 ‐(C,N)‐ OMe PDI‐H)Cl (PPh 3 ) 2 ] 0 ( 2 ), were studied. In octahedral complex 1 , bis(imino)pyridine (PDI) is a tridentate η 3 ‐N,N,N‐coordinated ligand, whereas in trigonal‐bipyramidal complex 2 , the deprotonated PDI ligand adopts the unusual bidentate binding mode η 2 ‐C,N to coordinate to the central Ru(II) ion. Bulk electrolysis in two electrolyte solutions of acetonitrile (MeCN) and tetrahydrofuran (THF) suggests that complexes 1 and 2 have very different electrocatalytic CO 2 reduction activities. In MeCN solution, complex 1 can selectively electrocatalytic CO 2 reduction to CO with a Faradaic efficiency of about 50% and a turnover frequency (TOF) of 4.4 s −1 , whereas complex 2 can perform electrocatalytic of CO 2 reduction with a Faraday efficiency of ~22% and a TOF of 0.3 S −1 . The electrocatalytic CO 2 reduction selectivity and activity of the two complexes are poor when the solvent is changed to THF. Combined with the results of the density functional theory calculation, we propose that the binding pattern of the redox‐active ligand OMe PDI has a significant effect on the electrocatalytic activity for the two Ru(II)PDI complexes.