566921-50-4Relevant articles and documents
Chemical oxidation of ferrocenyl(phenyl)phosphines and ferrocenyl(phenyl)phosphine chalcogenides
Verschoor-Kirss, Michael J.,Hendricks, Olivia,Verschoor, Carla M.,Conry, Rebecca,Kirss, Rein U.
, p. 30 - 38 (2016/10/04)
The electrochemistry of ferrocene-substituted phosphines suggests electron loss from a largely ferrocene-based HOMO with significant phosphorus character rather than the exclusive oxidation of iron. In contrast, studies of the chemical oxidation of ferrocenylphosphines are limited. Reactions between FcPPh2(1) and silver salts (AgCF3CO2, AgBF4, and AgOTf) lead to the silver-phosphine complexes [(FcPPh2)2Ag][CF3CO2] (11), [(FcPPh2)3Ag][BF4] (13), and [(FcPPh2)3Ag][OTf] (16), respectively, with no evidence for oxidation of FeIIto FeIII. Compound 13 reacts with traces of water forming FcP(OBF3)Ph2(15) which crystallizes in the P1ˉ space group with a?=?10.326(4)??, b?=?10.326(4)??, c?=?17.445(6)??, α?=?104.068(6)°, β?=?99.970(7)°, and γ?=?100.542(7)°. Reaction of 1 with excess AgOTf, however, yields a green, paramagnetic, FeIIIcomplex: [(FcPPh2)Ag][OTf]2(17) based on elemental analysis, ESR and M?ssbauer spectroscopy. Reaction of 1 with bromine yields paramagnetic FcPPh2Br3(10) by ESR spectroscopy. Reactions between ferrocenyl(phenyl)phosphines, FcnPPh3–n(1–3, Fc?=?C5H5FeC5H4, n?=?1–3), and sulfur or selenium yield the corresponding ferrocenyl(phenyl)-phosphine chalcogenides, FcnP(E)Ph3–n(4–9, n?=?1–3, E?=?S, Se). The crystal structures of (FcP(S)Ph2(4) are reported; P21/c space group, a?=?14.5187(16)??, b?=?10.5915(12)??, c?=?12.0004(13)??, α?=?90°, β?=?96.891(2)°, γ?=?90°. Reaction of 4 with bromine is accompanied by the loss of sulfur also yields 10.
Electron-donating ability of triarylphosphines and related compounds studied by 31P NMR spectroscopy
Chevykalova,Manzhukova,Artemova,Luzikov,Nifant'ev,Nifant'ev
, p. 78 - 84 (2007/10/03)
The influence of aryl, heterocyclic, amide, alkyl, alkoxyl, thioalkoxyl, and ferrocenyl substituents at the phosphorus atom on its electron-donating ability was studied by the measurement of direct 31P-77Se spin-spin coupling constants for the corresponding selenides. Series of diphenylorganylphosphines and their selenides were studied.
