Diiron complexes with bridging hydrocarbyl ligands and containing CO and Cp ligands (Cp = η5-C5H5) have been investigated as possible electrocatalysts for H2 production. In particular, studies included the vinyliminium complexes [Fe2{μ-η1:η3-C(R′)=CRCNMe2}(μ-CO)(CO)- (Cp)2][SO3CF3] (R′ = Tol (4-MeC6H4), R = H, 1a; R′ = CH2OH, R = H, 1b; R′ = CH2OH, R = SPh, 1c), the vinylalkylidene [Fe2{μ-η1:η3- C(Tol)CHCHNMe2}(μ-CO)(CO)(Cp)2] (2), the aminoalkylidyne [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(L)(Cp)2][SO3CF3] (R = Me, L = CO, 3a; R = Me, L = NCMe, 3b; R = Xyl (2,6-Me2C6H3), L = CO, 3c), [Fe2{μ- CN(Me)2}(μ-L′)(CO)(L)(Cp)2] (L′ = CO, L = CN, 4; L′ = H, L = CO, 5), the thiocarbyne complexes [Fe2(μ-CSEt)(μ-CO)(CO)2(Cp)2][BF4], (6) and [Fe2(μ-CSMe)(μ-CO)(CO)(CN)(Cp)2] (7), and the alkylidene complexes [Fe2{μ-C(CN)(SMe)}(μ-CO)(CO)2(Cp)2][SO3CF3] (8) and [Fe2{μ-C(CN)(PMe2Ph)}(μ-CO)(CO)2(Cp)2][SO3CF3] (9). Cyclic voltammograms (CV) of the above complexes in CH3CN have been recorded in the presence of increasing amounts of acetic acid to evidence electrocatalytic proton reduction. In spite of the fact that the above diiron complexes do not resemble the typical diiron dithiolate model systems, the aminocarbyne 4 and the thiocarbyne complex 7 exhibit significant electrocatalytic properties for proton reduction (e.g., for 4, the turnover number (TON) is 15.5).
Mazzoni, R., Gabiccini, A., Cesari, C., Zanotti, V., Gualandi, I., Tonelli, D. (2015). Diiron Complexes Bearing Bridging Hydrocarbyl Ligands as Electrocatalysts for Proton Reduction. ORGANOMETALLICS, 34(13), 3228-3235 [10.1021/acs.organomet.5b00274].
Diiron Complexes Bearing Bridging Hydrocarbyl Ligands as Electrocatalysts for Proton Reduction
MAZZONI, RITA;GABICCINI, ALBERTO;CESARI, CRISTIANA;ZANOTTI, VALERIO;GUALANDI, ISACCO;TONELLI, DOMENICA
2015
Abstract
Diiron complexes with bridging hydrocarbyl ligands and containing CO and Cp ligands (Cp = η5-C5H5) have been investigated as possible electrocatalysts for H2 production. In particular, studies included the vinyliminium complexes [Fe2{μ-η1:η3-C(R′)=CRCNMe2}(μ-CO)(CO)- (Cp)2][SO3CF3] (R′ = Tol (4-MeC6H4), R = H, 1a; R′ = CH2OH, R = H, 1b; R′ = CH2OH, R = SPh, 1c), the vinylalkylidene [Fe2{μ-η1:η3- C(Tol)CHCHNMe2}(μ-CO)(CO)(Cp)2] (2), the aminoalkylidyne [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(L)(Cp)2][SO3CF3] (R = Me, L = CO, 3a; R = Me, L = NCMe, 3b; R = Xyl (2,6-Me2C6H3), L = CO, 3c), [Fe2{μ- CN(Me)2}(μ-L′)(CO)(L)(Cp)2] (L′ = CO, L = CN, 4; L′ = H, L = CO, 5), the thiocarbyne complexes [Fe2(μ-CSEt)(μ-CO)(CO)2(Cp)2][BF4], (6) and [Fe2(μ-CSMe)(μ-CO)(CO)(CN)(Cp)2] (7), and the alkylidene complexes [Fe2{μ-C(CN)(SMe)}(μ-CO)(CO)2(Cp)2][SO3CF3] (8) and [Fe2{μ-C(CN)(PMe2Ph)}(μ-CO)(CO)2(Cp)2][SO3CF3] (9). Cyclic voltammograms (CV) of the above complexes in CH3CN have been recorded in the presence of increasing amounts of acetic acid to evidence electrocatalytic proton reduction. In spite of the fact that the above diiron complexes do not resemble the typical diiron dithiolate model systems, the aminocarbyne 4 and the thiocarbyne complex 7 exhibit significant electrocatalytic properties for proton reduction (e.g., for 4, the turnover number (TON) is 15.5).File | Dimensione | Formato | |
---|---|---|---|
Organometallics 2015.pdf
accesso aperto
Tipo:
Postprint
Licenza:
Licenza per accesso libero gratuito
Dimensione
920.25 kB
Formato
Adobe PDF
|
920.25 kB | Adobe PDF | Visualizza/Apri |
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.