Synthesis, structure, and electrochemical properties of 4,5-diaryl-1,2,3-triphosphaferrocenes and the first example of multi(phosphaferrocene)

Abstract

Reaction between aryl substituted sodium 1,2,3-triphospholides or bis-1,2,3-triphospholide and [Fe(η6-(C6H5CH3)Cp]+[PF6]- in boiling diglyme results in pure 1,2,3-triphosphaferrocenes 1-3 or bis-(1,2,3-triphosphaferrocene) 4, respectively, with good yields. The structure of all obtained...

Synthesis, structure and electrochemical properties of 3,4,5-triaryl-1,2-diphosphaferrocenes

“…Recently, we have reported a convenient and effective method for the preparation of heteroleptic 1,2,3-triphosphaferrocenes. 26 Using this approach, sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide 1 was reacted with [FeCp(η 6 -C 6 H 5 CH 3 )][PF 6 ] in a 1 : 1 ratio in boiling diglyme. Workup including evaporation of diglyme, extraction of the product with toluene followed by filtration through a silica gel layer furnished 3,4,5-triaryl-1,2-diphosphaferrocenes 2 in good yields (up to 78%) and high purity.…”

“…31 Bond angles and bond lengths in the cyclo -P 2 C 3 ring in 2 are comparable to those in 4,5-diaryl-1,2,3-triphosphaferrocenes. 26…”

“…Among phosphaferrocenes, 1-mono-, 25 1,2,3-tri-, 26,27 1,2,4-tri- 28 and pentaphosphaferrocene 24,29 derivatives are currently the most investigated. In contrast, 1,2-diphosphaferrocenes have received comparatively less attention due to the absence of simple and effective rational synthetic routes, as the only known approaches are associated with multistep synthesis, side reactions and moderate yields (12–28%).…”

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

“…+147 and +160 ppm for the heteroaromatic P2C3 ring backbone. Recently, we have reported a convenient method for the preparation of 1,2diphosphaferrocenes [37] and 1,2,3-triphosphaferrocenes [25] with various substituents at para-positions of aryl groups. Using this approach, sodium 3,4,5-tris(3-chlorophenyl)- ring and a singlet at about 75 ppm for the cyclopentadienyl ring.…”

“…Various effective synthetic approaches were developed for 1-mono- [22,23,24], 1,2,3-tri- [25,26,27], 1,2,4-tri- [28,29,30], and pentaphosphaferrocenes [31,32,33], whereby their chemistry is most investigated and well represented at present time. In contrast, very limited data are available concerning 1,2-diphosphaferrocenes due to the absence of simple and effective routes to their synthesis [34,35,36].…”