Electrochemical Properties and Structure of Multi-Ferrocenyl Phosphorus Thioesters

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.

Synthesis, characterization and electrochemical behavior of new bis(fluoroalkyl) ferrocenylphosphonates and their tin tetrachloride complexes

“…4). This trend is in general consistent with related ferrocenyl phosphonates [24]. The low energy absorption is most probably assigned to ferrocene [42].…”

“…On the other hand, ferrocene and ferrocenyl derivatives are well known for their ability to undergo reversible one-electron oxidation, they have been used extensively as single-electron transfer (SET) reagents in organometallic and coordination chemistry to switch the redox state of complexes [19][20][21][22]. Ferrocenene-containing organophosphorus compounds are increasingly investigated in organic synthesis as synthetic intermediates [23,24], potential ligands, in catalysis [25] and as sensitizers in dye sensitized solar cells [26].…”

Comparison of crystal structure and DFT calculation of triferrocenyl trithiophosphite’s conformation

“…gauche-configuration of alkyl(aryl)thio groups has been observed for free trithiophosphites even in solid state [7] or in gas phase [8][9][10].…”

“…It should be noted that with the exception of tertiary phosphines, a relatively small number of trivalent phosphorus derivatives have been used to construct multiferrocene compounds. The use of ferrocene derivatives containing a phosphorus-sulfur bond is a promising direction, since coordination with a metal atom can occur both at the phosphorus and sulfur atoms [7]. To obtain such complexes it is important to know the conformational capabilities of the ligand [8][9][10][11].…”

The core of the matter – arene substitution determines the coordination and catalytic behaviour of tris(1-phosphanyl-1′-ferrocenylene)arene gold(i) complexes

“…Table S3 †) are closer to the ideal 180°t han those found in [1b(Au)]OTf, most likely because the 1,3,5-tris(ferrocenyl)arene-derived ligand structure itself does not impose any steric restrictions anymore. The individual Even though the formation of this CP was not intended and its preparation suffers from poor reproducibility, redox-active ferrocene-derived CPs have recently attained great interest for the insight into molecular architecture and self-assembly [75][76][77] they provide as well as for their potential applications in catalysis, 78,79 non-linear optics, and molecular magnetism. 77 Following the classification of Mochida, {[(1c) 2 (Au) 3 ](OTf ) 3 } n is a one-dimensional main-chain CP derived from a neutral ligand.…”