| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1305367 | Inorganica Chimica Acta | 2016 | 9 Pages |
•FcPPh2 reacts with silver salts yielding diamagnetic, silver-phosphine complexes.•FcPPh2 reacts with excess AgOTf, yielding a green, paramagnetic, FeIII complex.•Reaction of [(FcPPh2)3Ag][BF4] with traces of water yields FcP(OBF3)Ph2.•FcnPPh3–n (n = 1–3), react with S or Se yield ferrocenyl(phenyl)phosphine chalcogenides.•Reactions between FcPPh2 or FcP(S)Ph2 and bromine yield FcPPh2Br3.
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 FeII to FeIII. Compound 13 reacts with traces of water forming FcP(OBF3)Ph2 (15) which crystallizes in the P1¯ space group with a = 10.326(4) Å, b = 10.326(4) Å, c = 17.445(6) Å, α = 104.068(6)°, β = 99.970(7)°, and γ = 100.542(7)°. Reaction of 1 with excess AgOTf, however, yields a green, paramagnetic, FeIII complex: [(FcPPh2)Ag][OTf]2 (17) based on elemental analysis, ESR and Mössbauer 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) Å, b = 10.5915(12) Å, c = 12.0004(13) Å, α = 90°, β = 96.891(2)°, γ = 90°. Reaction of 4 with bromine is accompanied by the loss of sulfur also yields 10.
Graphical abstractReaction of FcPPh2 (1) with AgCF3CO2 or AgOTf yields the silver-phosphine complexes [(FcPPh2)2Ag][CF3CO2] (11) and [(FcPPh2)3Ag][OTf] (16), respectively. Reaction with excess AgOTf, however, yields a green, paramagnetic, FeIII complex: [(FcPPh2)Ag][OTf]2 (17) by ESR and Mossbauer spectroscopy.Figure optionsDownload full-size imageDownload as PowerPoint slide
