Premium
Synthetic and Structural Studies on a New Type of [Fe]‐Hydrogenase Mimics Each Containing One Hantzsch Ester Moiety
Author(s) -
Song LiCheng,
Liu BeiBei,
Xu KaiKai
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000523
Subject(s) - chemistry , moiety , medicinal chemistry , pyridine , stereochemistry
To develop the synthetic methodology for [Fe]‐H 2 ase models, a new type of the Hantzsch ester moiety‐containing [Fe]‐H 2 ase models ( 1–7 ) has been synthesized on the basis of preparing a series of new 2,6‐disubstituted pyridine precursors (L 1–L10 ). Thus, the iodo models [2‐COCH 2 ‐6‐(HEH)C 5 H 3 N]Fe(CO) 2 I ( 1 ), {2‐COCH 2 ‐6‐[C 6 H 4 (HEH)]C 5 H 3 N}Fe(CO) 2 I ( 2 ), and {2‐COCH 2 ‐6‐[Me(HEH)]C 5 H 3 N}Fe(CO) 2 I ( 3 ) could be prepared by reactions of precursors 2‐TsOCH 2 ‐6‐(HEH)C 5 H 3 N ( L2 ), 2‐TsOCH 2 ‐6‐[C 6 H 4 (HEH)]C 5 H 3 N ( L6 ), and 2‐TsOCH 2 ‐6‐[Me(HEH)]C 5 H 3 N ( L10 ) with Na 2 Fe(CO) 4 followed by treatment of the resulting Fe(0) intermediates M1 , M2 and M3 with iodine, respectively. In addition, further treatment of model 1 with AgOTf followed by reaction of the resulting Fe(II) intermediate M4 with MeCN gave the MeCN‐coordinated model {[2‐COCH 2 ‐6‐(HEH)C 5 H 3 N]Fe(CO) 2 (MeCN)}(OTf) ( 4 ), whereas reaction of precursor L2 with Na 2 Fe(CO) 4 followed by treatment of intermediate M1 with dimers (RCO 2 ) 2 afforded benzoato models [2‐COCH 2 ‐6‐(HEH)C 5 H 3 N]Fe(CO) 2 (O 2 CR) ( 5 , R = 4‐ClC 6 H 4 ; 6 , 2,6‐F 2 C 6 H 3 ; 7 , 2‐F 3 CC 6 H 4 ). All the new precursors L1 – L10 and models 1 – 7 were characterized by various spectroscopic methods and for some of them by X‐ray crystallography.