Chemical oxidation of ferrocenyl(phenyl)phosphines and ferrocenyl(phenyl)phosphine chalcogenides

Autor: Rebecca R. Conry, Olivia Hendricks, Michael J. Verschoor-Kirss, Rein U. Kirss, Carla M. Verschoor
Rok vydání: 2016
Předmět:
Zdroj: Inorganica Chimica Acta. 450:30-38
ISSN: 0020-1693
DOI: 10.1016/j.ica.2016.05.010
Popis: 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 P 1 ¯ space group with a = 10.326(4) A, b = 10.326(4) A, c = 17.445(6) A, 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 Mossbauer 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) A, b = 10.5915(12) A, c = 12.0004(13) A, α = 90°, β = 96.891(2)°, γ = 90°. Reaction of 4 with bromine is accompanied by the loss of sulfur also yields 10.
Databáze: OpenAIRE
Externí odkaz: