Synthesis, structure and electrochemical properties of 3, 4, 5-triaryl-1, 2-diphosphaferrocenes. Issue 11 (21st April 2022)

• Record Type: Journal Article
• Authors: Bezkishko, Ilya A.; Zagidullin, Almaz A.; Khrizanforov, Mikhail N.; Gerasimova, Tatiana P.; Ivshin, Kamil A.; Kataeva, Olga N.; Ganushevich, Yulia S.; Miluykov, Vasili A.; Lönnecke, Peter; Hey-Hawkins, Evamarie
• Is Part Of: Inorganic chemistry frontiers. Volume 9:Issue 11(2022)
• Page Start: 2608
• Page End: 2616
• Publication Date: 2022-04-21
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2qi00446a
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : New 3, 4, 5-triaryl-1, 2-diphosphaferrocenes [FeCp(η 5 -P2 C3 R3 )] have been extensively studied experimentally (NMR, UV-Vis, electrochemical studies, X-ray) and quantum chemically. Abstract : Aryl-substituted sodium 1, 2-diphosphacyclopentadienides Na(P2 C3 R3 ) (R = Ph, 4-Me-C6 H4, 4-Cl-C6 H4 )(1a-c ) react with [FeCp(η 6 -C6 H5 CH3 )][PF6 ] to give heteroleptic 3, 4, 5-triaryl-1, 2-diphosphaferrocenes [FeCp(η 5 -P2 C3 R3 )] (2a-c ) in 71–78% yield. The structures of 2a-c were confirmed by NMR, UV-Vis spectroscopy and X-ray structure analysis, and supported by DFT calculations. Electrochemical studies of 2a-c in CH3 CN demonstrate a pronounced reversible one-electron oxidation, while in the solid state, all 3, 4, 5-triaryl-1, 2-diphosphaferrocenes show fully reversible oxidation and reduction waves, which indicates the stability of the oxidized form. Regardless of the substituent (R = Ph, 4-Me-C6 H4, 4-Cl-C6 H4 ), the studied 1, 2-diphosphaferrocenes have similar oxidation and reduction potentials.