Abstract
Metallocenes [Ti](Cl)(OFc) (4) and [M](EFc)(2) {[M] = M((5)-C5H5)(2); M = Ti: 5a, E = O; 5b, E = S; 5c, E = Se. M = Zr: 6, E = O; Fc = Fe((5)-C5H4)((5)-C5H5)} were prepared by the treatment of [M]Cl-2 (1, M = Ti; 2, M = Zr) with FcOLi (3), or by the reaction of FcELi (8a, E = S; 8b, E = Se) with 1. The solid-state structures of the metallocenes 4, 5a,b, and 6 are reported. The electrochemical (4, 5a,b,c) and spectroelectrochemical (in situ UV/Vis/NIR) [5a, Fc(2)E(2) for comparison; E = S (9), Se (10)] behavior is discussed. All Ti compounds show irreversible Ti-IV/Ti-III reduction processes at E-pc = -1520 to -2100 mV. Reversible Fc redox processes are characteristic for 4 (E-1 degrees = -308 mV) and 5a (E-1 degrees = -429, E-2 degrees = -142 mV). For 5b three processes at E-1 degrees = -151, E-2 degrees = 87, and E-3 degrees = 369 mV are found. In multicyclic CV studies it could be shown that after Ti-IV/Ti-III reduction the Ti-S bonds in 5b were cleaved resulting in the formation of Fc(2)S(2) (9), which shows two separate reversible redox processes at E-1 degrees = 64 and E-2 degrees = 366 mV for the Fc groups. However, metallocene 5c decomposes in solution producing 10. UV/Vis/NIR studies on 5a, 9, and 10 indicate significant electrostatic interaction among the Fc/Fc(+) groups as oxidation progresses.
| Original language | English |
|---|---|
| Pages (from-to) | 3156-3163 |
| Number of pages | 8 |
| Journal | European Journal of Inorganic Chemistry |
| Issue number | 27 |
| DOIs | |
| Publication status | Published - 23 Jul 2018 |
| Externally published | Yes |
Cite this
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Synthesis and Electrochemical Behavior of Ferrocenyl-Functionalized Metallocenes M((5)-C5H5)(2)(EFc)(2) (M = Ti, Zr; E = O, S, Se). / Frenzel, Peter; Korb, Marcus; Hildebrandt, Alexander; Lang, Heinrich.
In: European Journal of Inorganic Chemistry, No. 27, 23.07.2018, p. 3156-3163.Research output: Contribution to journal › Article
TY - JOUR
T1 - Synthesis and Electrochemical Behavior of Ferrocenyl-Functionalized Metallocenes M((5)-C5H5)(2)(EFc)(2) (M = Ti, Zr; E = O, S, Se)
AU - Frenzel, Peter
AU - Korb, Marcus
AU - Hildebrandt, Alexander
AU - Lang, Heinrich
PY - 2018/7/23
Y1 - 2018/7/23
N2 - Metallocenes [Ti](Cl)(OFc) (4) and [M](EFc)(2) {[M] = M((5)-C5H5)(2); M = Ti: 5a, E = O; 5b, E = S; 5c, E = Se. M = Zr: 6, E = O; Fc = Fe((5)-C5H4)((5)-C5H5)} were prepared by the treatment of [M]Cl-2 (1, M = Ti; 2, M = Zr) with FcOLi (3), or by the reaction of FcELi (8a, E = S; 8b, E = Se) with 1. The solid-state structures of the metallocenes 4, 5a,b, and 6 are reported. The electrochemical (4, 5a,b,c) and spectroelectrochemical (in situ UV/Vis/NIR) [5a, Fc(2)E(2) for comparison; E = S (9), Se (10)] behavior is discussed. All Ti compounds show irreversible Ti-IV/Ti-III reduction processes at E-pc = -1520 to -2100 mV. Reversible Fc redox processes are characteristic for 4 (E-1 degrees = -308 mV) and 5a (E-1 degrees = -429, E-2 degrees = -142 mV). For 5b three processes at E-1 degrees = -151, E-2 degrees = 87, and E-3 degrees = 369 mV are found. In multicyclic CV studies it could be shown that after Ti-IV/Ti-III reduction the Ti-S bonds in 5b were cleaved resulting in the formation of Fc(2)S(2) (9), which shows two separate reversible redox processes at E-1 degrees = 64 and E-2 degrees = 366 mV for the Fc groups. However, metallocene 5c decomposes in solution producing 10. UV/Vis/NIR studies on 5a, 9, and 10 indicate significant electrostatic interaction among the Fc/Fc(+) groups as oxidation progresses.
AB - Metallocenes [Ti](Cl)(OFc) (4) and [M](EFc)(2) {[M] = M((5)-C5H5)(2); M = Ti: 5a, E = O; 5b, E = S; 5c, E = Se. M = Zr: 6, E = O; Fc = Fe((5)-C5H4)((5)-C5H5)} were prepared by the treatment of [M]Cl-2 (1, M = Ti; 2, M = Zr) with FcOLi (3), or by the reaction of FcELi (8a, E = S; 8b, E = Se) with 1. The solid-state structures of the metallocenes 4, 5a,b, and 6 are reported. The electrochemical (4, 5a,b,c) and spectroelectrochemical (in situ UV/Vis/NIR) [5a, Fc(2)E(2) for comparison; E = S (9), Se (10)] behavior is discussed. All Ti compounds show irreversible Ti-IV/Ti-III reduction processes at E-pc = -1520 to -2100 mV. Reversible Fc redox processes are characteristic for 4 (E-1 degrees = -308 mV) and 5a (E-1 degrees = -429, E-2 degrees = -142 mV). For 5b three processes at E-1 degrees = -151, E-2 degrees = 87, and E-3 degrees = 369 mV are found. In multicyclic CV studies it could be shown that after Ti-IV/Ti-III reduction the Ti-S bonds in 5b were cleaved resulting in the formation of Fc(2)S(2) (9), which shows two separate reversible redox processes at E-1 degrees = 64 and E-2 degrees = 366 mV for the Fc groups. However, metallocene 5c decomposes in solution producing 10. UV/Vis/NIR studies on 5a, 9, and 10 indicate significant electrostatic interaction among the Fc/Fc(+) groups as oxidation progresses.
KW - Metallocenes
KW - Ferrocene
KW - Electrochemistry
KW - Solid-state structures
KW - SOLID-STATE STRUCTURE
KW - ELECTRONIC COMMUNICATION
KW - NONAQUEOUS SOLVENTS
KW - MOLECULAR-STRUCTURE
KW - DELTA-E-1/2 VALUES
KW - CYCLIC VOLTAMMETRY
KW - COMPLEXES
KW - TITANIUM
KW - DERIVATIVES
KW - ZIRCONIUM
U2 - 10.1002/ejic.201800178
DO - 10.1002/ejic.201800178
M3 - Article
SP - 3156
EP - 3163
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1099-0682
IS - 27
ER -