m), 965 (m), 935 (w), 925 (w), 910 (w), 905 (w), 885 (m), 875 (w), 860 (w), 850 (s), 835 (s), 755 (w), 738 (m), 728 (m), 720 (m) cm-I.A yellow-brown band was eluted from the column in 60%CHzC12/hexane which upon rotary evaporation of solvent produced 60 mg (1.6%) of green-brown crystals of 111, (CSH5Fe)zC2B8H90H, mp >300 OC. Mass measurement calcd for 12C1z'H201'B856Fe2160+ 380.0957, found 380.0973; calcd for 12C1i13C'H~~'iB~57Fe2160+ 383.1000, found 383.1003. Infrared spectrum (NUJO~ mull): 3450 (w), 3090 (w), 2490 (vs), 1425 (m), 1415 (m), 1275 (m), 1150 (m), 1110 (s), 1070 (s), 1045 (w), 1020 (m), 1015 (m), 988 (m), 938 (w), 882 (m), 844 (s), 720 (w), 688 (m) cm-'.The silica gel was then extracted with CH3CN, yielding a deep green solution. Removal of CH3CN followed by addition of HzO, filtration, and addition of excess (CH3)4NC1 produced a green precipitate. The precipitate (150 mg) was dissolved in acetone and stripped onto silica gel and chromatographed on a 2 X 15 cm silica gel column. Elution with CH2C12 removed impurities while elution with 10% acetone/CH2Clz eluted the green band. Addition of 1propanol to the filtrate followed by slow rotary evaporation produced 84 mg (1.6%) of dark green crystals of 11, [(CH3)4N][C5HsFeC2-B9HIiFeC2B9fiil], mp >300 OC. (m), 995 (m), 977 (m), 950 (m), 883 (m), 860 (w), 840 (s), 760 (m), 740 (m), 724 (m) cm-I. Polyhedral Expansion of 1-(~s-C5H5)-1-Fe-2,3-CzB8Hlo. This reaction was performed as above with 0.98 g (4.06 mmol) of 1,-2,3-CSHSFeC2B8H10. To the reduced solution was added, as a solid, 6.5 g (19 mmol) of [CsH5FeC6H6][PF6]. The mixture was stirred 120 h under nitrogen and worked up as above. Elution of the chromatography column with hexane produced ferrocene, and elution with 20% CHzCl2-hexane yielded 60 mg of starting material. A red band eluted in CH2C12. Addition of a small amount of hexane followedInorganic Chemistry, Vol. 17, No. 6, 1978 1501 by rotary evaporation of the solvent produced 90 mg of red-purple crystals, mp >310 O C , whose mass and 'H NMR spectra were consistent with the formulation (CsH5Fe)2CZB8HI0. No 80.5-MHz "B NMR spectrum was observable for the paramagnetic species. The elemental analysis and magnetic susceptibility were close to that expected for CSH5FeC2B8Hlo, due presumably to solid-state decomposition.3, 291 (1973). (13) T. E. Paxson, M. K. Kaloustian, G. M. Tom, R.This paper reports the reactions of meso-tetraphenylporphyrin (TPPH2) with selected cations on the interlamellar surfaces of montmorillonite, a swelling layer lattice silicate related to mica. Strongly acidic hydrated Fe3+ and V 0 2 + ions react quantitatively with the free base porphyrin to afford the protonated porphyrin dication (TPPHZ+) in the form of intercalated monolayers. Monolayers of TPPH42+ are also formed by reaction of the free base porphyrin with hydronium ions on the silicate surfaces. Weakly acidic hydrated Na+ and Mg2+ on the surface-exchange sites afford only trace amounts of TPPHd2+.No porphyrin dication is formed with (n-C3H7)N+. Co2+, Cu2+, and Zn2+ reac...

Publication costs assisted by Michigan State UniversityThe adsorption of selected aromatic molecules on the intracrystal surfaces of Fe(II1) and VQ2+ exchange forms of a layer lattice silicate (hectorite) has been studied by ir, uv-visible, and esr spectroscopy. In addition to aromatic radical cation formation, type I1 species, which exhibit an intense charge-transfer band in the ir region and vibrational frequencies that are substantially shifted relative to the parent molecule, are formed with benzene on the Fe(II1) exchange form and with anisole and thiophene on both Fe(II1) and V02+ exchange forms. The complexes are identical with those previously observed on Cu(I1) layer lattice silicates. It is suggested that the type I1 species are associated radical cations formed by electron transfer from the parent molecule to the metal ion. Toluene radical cation formation is accompanied by polymerization, and the polymer apparently inhibits radical cation association. IntroductionIn an earlier report1 from these laboratories it was shown that the chemisorption of benzene on the interlamellar surfaces of copper(I1) montmorillonite under dehydrating conditions results in the formation of two distinct species distinguishable by infrared spectroscopy: a greenyellow type I complex containing a planar C6H6 ring, and

No abstract