Synthesis and Electrochemical Behavior of Ferrocenyl-Functionalized Metallocenes M((5)-C5H5)(2)(EFc)(2) (M = Ti, Zr; E = O, S, Se)

Peter Frenzel, Marcus Korb, Alexander Hildebrandt, Heinrich Lang

Research output: Contribution to journalArticle

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 languageEnglish
Pages (from-to)3156-3163
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number27
DOIs
Publication statusPublished - 23 Jul 2018
Externally publishedYes

Cite this

@article{08ba4d48717d45e28f07c10b0d405e92,
title = "Synthesis and Electrochemical Behavior of Ferrocenyl-Functionalized Metallocenes M((5)-C5H5)(2)(EFc)(2) (M = Ti, Zr; E = O, S, Se)",
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.",
keywords = "Metallocenes, Ferrocene, Electrochemistry, Solid-state structures, SOLID-STATE STRUCTURE, ELECTRONIC COMMUNICATION, NONAQUEOUS SOLVENTS, MOLECULAR-STRUCTURE, DELTA-E-1/2 VALUES, CYCLIC VOLTAMMETRY, COMPLEXES, TITANIUM, DERIVATIVES, ZIRCONIUM",
author = "Peter Frenzel and Marcus Korb and Alexander Hildebrandt and Heinrich Lang",
year = "2018",
month = "7",
day = "23",
doi = "10.1002/ejic.201800178",
language = "English",
pages = "3156--3163",
journal = "European Journal of Inorganic Chemistry",
issn = "1099-0682",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
number = "27",

}

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 journalArticle

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 -