title: Synthesis and redox properties of crowded triarylphosphines possessing ferrocenyl groups.
abstract: Crowded triarylphosphines possessing ferrocenyl groups [(4-ferrocenyl-2,6-diisopropylphenyl)(n)(2,4,6-triisopropylphenyl)(3-n)P (5a, n = 1; 5b, n = 2; 5c, n = 3)] were synthesized by the reaction of the corresponding arylcopper(I) reagents with the diarylchlorophosphines. Structures of the triarylphosphines were studied by 1H, 13C, and 31P NMR spectroscopies, and the characteristic patterns of the proton signals of the 2,6-isopropyl groups and upfielded 31P chemical shifts suggest structural similarities of the triarylphosphine moiety to the previously reported tris(2,4,6-triisopropylphenyl)phosphine (2). X-ray crystallography of 5c also revealed that the structure around the phosphorus is similar to that of 1, where the average bond angle and length around the phosphorus atom are 110.8 degrees and 1.854 A, respectively. According to the electrochemical measurements, phosphines 5a, 5b, and 5c are reversibly oxidized in two, three, and four steps, respectively, which suggests significant electronic interaction among the triarylphosphine and the ferrocene redox centers as well as weak interaction among the ferrocene redox centers. The EPR spectra obtained at cryogenic temperature after oxidation of phosphines 5a, 5b, and 5c are superpositions of those for the cation radicals of the crowded triarylphosphine and ferricinium. The solution spectra obtained at 293 K, which consist of two lines typical of the cation radical of the crowded triarylphosphines, become weaker as the number of the ferrocenyl groups increases and the cation radical of 5c does not show EPR signals. These findings suggest not only instability of the tetra(cation radical) of 5c but also the course of oxidation where the ferrocenyl groups in the periphery of the molecules are oxidized at first.
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, Aoba, Sendai 980-8578, Japan.
authors.forename: Katsuhide
authors.initials: K
authors.lastname: Sutoh
authors.forename: Shigeru
authors.initials: S
authors.lastname: Sasaki
authors.forename: Masaaki
authors.initials: M
authors.lastname: Yoshifuji
mesh_terms: D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D005296:Ferrous Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D000075163:Metallocenes; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry*; D012680:Sensitivity and Specificity
chemical_list: D005296:Ferrous Compounds; D000075163:Metallocenes; D009942:Organometallic Compounds; D010720:Phosphines; C004998:ferrocene