Electrochemical Properties and Structure of Multi-Ferrocenyl Phosphorus Thioesters.

Aleksandr Kononov,Vasily Miluykov,Mikhail Khrizanforov,Tatiana Gerasimova,Olga Kataeva,Yulia Budnikova,Zilya Yamaleeva,Alyona Lakomkina,Kamil Ivshin,Ruslan Shekurov,Oleg Sinyashin,Ilya Bezkishko

doi:10.3390/molecules25040939

Abstract

The reaction of triferrocenylthiophosphite with elemental sulfur leads to triferrocenyltetrathiophosphate. The molecule of tetrathiophosphate adopts propeller-like all synclinal-conformation of the ferrocenyl fragments respective to the P=S bond. All ferrocenyl groups have nearly ideal eclipsed conformation of the cyclopentadienyl fragments. The Fc3S3P (1), Fc3S3P=O, (2) and Fc3S3P=S (3) demonstrate three reversible and well-separated ferrocenyl-based redox events. The electronic structures of 1–3 have been studied quantum-chemically; the energies and composition of frontier orbitals have been calculated.

Highlights

A number of new practical applications of multi-ferrocenyl compounds are being actively developed. [1,2,3,4,5,6,7,8,9,10,11] The multi-ferrocenes are widely used as model systems for understanding intramolecular charge transfer processes
AllAll thethe work ofthe theinitial initial reagents, synthesis, the release workrelated relatedto to the the preparation preparation of reagents, thethe synthesis, and and the release of of products wascarried carriedout outinin inert atmosphere using standard
Three reversible one-electron peaks corresponding to the stepwise oxidation of three ferrocene fragments are observed in the cyclic voltammograms of oxidation of 1, and the first oxidation potential is almost identical to free ferrocene

Summary

Introduction

A number of new practical applications of multi-ferrocenyl compounds are being actively developed. [1,2,3,4,5,6,7,8,9,10,11] The multi-ferrocenes are widely used as model systems for understanding intramolecular charge transfer processes. A number of new practical applications of multi-ferrocenyl compounds are being actively developed. More and more multi-ferrocenes are synthesized to study their charge transfer processes and to match intramolecular charge transfer interactions numbers. The approach based on the construction of multi-ferrocenyl compounds using spacers capable of transmitting exchange interactions was successfully implemented to obtain new practically significant materials. The disadvantage of this approach is the complexity of creating multi-ferrocene molecules, since the syntheses proceeds in several stages and, as a rule, with low yields. An alternative way to multi-ferrocenyl compound is using phosphorus acids derivatives, containing ferrocene fragments. These ferrocene derivatives can be accessed via low cost syntheses with good yields [14,15]. It was demonstrated that ferrocene containing phosphate molecules can be successfully used for the construction of multi-step multi-electron redox systems [16,17,18,19]

Methods

Results

Conclusion