Synthesis, characterization, and some properties of two types of new [Fe]-H2ase models containing a 4-phosphatopyridine or a 4-phosphatoguanosinepyridine moiety. (23rd October 2020)

• Record Type: Journal Article
• Authors: Song, Li-Cheng; Chen, Wei; Zhu, Liang; Hu, Fu-Qiang; Jiang, Kai-Yu
• Is Part Of: New journal of chemistry. Volume 44:Number 42(2020)
• Page Start: 18496
• Page End: 18507
• Publication Date: 2020-10-23
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d0nj04194g
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : The novel [Fe]-H2 ase active site framework-containing model 6 was first prepared and structurally characterized. Abstract : Two types of new [Fe]-H2 ase models were synthesized using well-designed synthetic methods. The first type of trisubstituted pyridine ligand-containing models [2-MeOCH2 -4-O2 P(OPh)2 -6-COCH2 C5 H2 N]Fe(CO)2 R (1, R = I; 2, R = EtS, 3, R = MeCOS), [2-MeOCH2 -4-O2 P(OPh)2 -6-COCH2 C5 H2 N]Fe(CO)2 (MeCN)BF4 (4 ) and [2-MeOCH2 -4-O2 P(OPh)2 -6-COCH2 C5 H2 N]Fe(CO)(PPh3 )I (5 ) were synthesized on the basis of preparing the new trisubstituted pyridine precursors L1 –L6, whereas the second type of pentasubstituted pyridine ligand-containing model [2-MeO-3, 5-Me2 -4-OPO(OPh)O-5′-( N 2-i PrCO-2′, 3′-O-CMe2 -guanosine)-6-COCH2 C5 N]Fe(CO)2 (η 2 -6-Me-2-SC5 H3 N) (6 ) was synthesized via the esterification reaction of a new phosphatoguanosine derivative L7 with the corresponding pentasubstituted pyridine ligand-containing precursor (2-MeO-4-HO-3, 5-Me2 -6-COCH2 C5 N)Fe(CO)2 (η 2 -6-Me-2-SCH5 H3 N) (D ) in the presence of the dehydrating agent DCC. While all the new precursors L1 –L7 and models 1–6 were fully characterized via elemental analysis and various spectroscopic techniques, the molecular structures of model 5 and precursor D were confirmed via X-ray crystallography. In addition, model 1 has been found to be a catalyst for proton reduction to H2 from TFA under CV conditions.