Aryl-substituted sodium 1,2-diphosphacyclopentadienides Na(P_(2)C_(3)R_(3))(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4))(1a-c)react with[FeCp(η^(6)-C_(6)H_(5)CH_(3))][PF6]to give heteroleptic 3,4,5-triaryl-1,2-diphosphaferr...Aryl-substituted sodium 1,2-diphosphacyclopentadienides Na(P_(2)C_(3)R_(3))(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4))(1a-c)react with[FeCp(η^(6)-C_(6)H_(5)CH_(3))][PF6]to give heteroleptic 3,4,5-triaryl-1,2-diphosphaferrocenes[FeCp(η^(5)-P_(2)C_(3)R_(3))](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 CH3CN 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-C_(6)H_(4),4-Cl-C_(6)H_(4)),the studied 1,2-diphosphaferrocenes have similar oxidation and reduction potentials.展开更多
基金funded by the grant of the Russian Science Foundation,grant number 21-73-10204The authors gratefully acknowledge the Assigned Spectral-Analytical Center of FRC Kazan Scientific Center of RAS(NMR,X-ray,electrochemical measurements)and the scholarship program of the German Academic Exchange Service(DAAD,X-ray structure determination of 2b)Y.S.G.is grateful for the support of the Ministry of Science and Higher Education of the Russia Federation.
文摘Aryl-substituted sodium 1,2-diphosphacyclopentadienides Na(P_(2)C_(3)R_(3))(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4))(1a-c)react with[FeCp(η^(6)-C_(6)H_(5)CH_(3))][PF6]to give heteroleptic 3,4,5-triaryl-1,2-diphosphaferrocenes[FeCp(η^(5)-P_(2)C_(3)R_(3))](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 CH3CN 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-C_(6)H_(4),4-Cl-C_(6)H_(4)),the studied 1,2-diphosphaferrocenes have similar oxidation and reduction potentials.
