Synthesis and electrochemical properties of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes

Abstract

A novel representative of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide containing a chloro substituent in the meta-position of the aryl groups was obtained with a high yield based on the reaction of tributyl(1,2,3-triarylcyclopropenyl)phosphonium bromide and sodium polyphosphides. Further reaction of sodium 3,4,5-tris(3-chlorophenyl)-1,2-diphosphacyclopentadienide with [FeCp(η6-C6H5CH3)][PF6] complex gives a new 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene. The electrochemical properties of 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene were studied and compared to 3,4,5-tris(4-chlorophenyl)-1,2-diphosphaferrocene. It was found that the position of the chlorine atom on the aryl fragment has an influence on the reduction potential of 1,2-diphosphaferrocenes, while the oxidation potentials do not change.

Synthesis, Structure, and Electrochemical Properties of 2,3,4,5-Tetraphenyl-1-Monophosphaferrocene Derivatives

“…Existing synthetic methods allow various phospholide anions to be obtained in their pure form, without PhLi impurities [ 4 , 28 ]. We have recently reported a convenient and effective method for the preparation of heteroleptic 1,2-diphosphaferrocenes [ 29 , 30 ] and 1,2,3-triphosphaferrocenes [ 31 , 32 ] through the reaction of appropriate 1,2-diphospholide- or 1,2,3-triphospholide anions in their pure form with a [(η 6 -toluene)FeCp]PF 6 complex. In the present article, we describe the rational and atom-economical synthesis of 2,3,4,5-tetraphenyl-1-monophosphaferrocene and its W(CO) 5 complex and compare their structural and electrochemical properties with the previously known analogues.…”

Effect of Phosphorus Substitution in the Cyclopentadienyl Ring of Ferrocene: Combined Mössbauer Spectroscopy and DFT Studies

“…Typical Experimental Synthetic Procedure for the Synthesis of Phosphaferrocenes 1−4. Recently, we have reported a convenient and effective method for the preparation of heteroleptic 1,2diphospha- 40,41 and 1,2,3-triphosphaferrocenes 42,43 by the reaction of the appropriate phosphacyclopentadienide anion with the [(C 6 H 5 CH 3 )Fe(C 5 H 5 )] + [PF 6 ] − complex. Using this approach phenyl-substituted 1-monophosphaferrocene (1), 1,2-diphosphaferrocene (2), and 1,2,3-triphosphaferrocenes (3,4) were synthesized in good yields (63−77%) and high purity (Scheme 1).…”

Organophosphorus chemistry: from model to application

“…In another study, the synthesis of bis(chlorophenyl)acetylenes that were useful for the preparation of 1,2,3-tris(chlorophenyl)cyclopropenylium bromides was accomplished [ 3 ]. The latter species were converted to tributyl(1,2,3-tris(chlorophenyl)cyclopropenyl)phosphonium bromides, affording 3,4,5-tris(chlorophenyl)-1,2-diphosphacyclopentadienides upon reaction with polyphosphides.…”