Organometallic cation-exchanged phyllosilicates: exchange with cations derived from (CH3)2SnCl2

Abstract Complexes formed between 0·034 m dimethyltin dichloride solutions and Na-montmorillonite at pH 2·4 and 4·0 have been characterized using 119Sn Mössbauer spectroscopy, X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and water sorption isotherms. The dominant exchange cation at pH 2·4 is Me2Sn2+ characterized by an isomer shift, δ, and quadrupole splitting, Δ values of 1·25 and 3·80 mm s−1, respectively. The major exchange cation at pH 4·0 is the dimer, [Me2SnOH]2 2+, (δ = 1·38, Δ = 3·34 mm s−1) although the monomer, Me2Sn(OH)+, (δ = 0·95, Δ = 3·29 mm s−1) is also present. These complexes have basal spacings of 15·0 and 16·0 Å, respectively, which are stable up to 200°C. Mössbauer spectroscopy has shown that these ions are converted to SnO2 via Me2SnO upon thermal degradation. The temperature at which these oxides appear coincides with the collapse of the basal spacing. Both complexes display BET Type IV isotherms for the adsorption of water, following thermal pretreatment at 150°C, but the complex prepared at pH 4·0 has a lower sorption capacity. Both complexes, contrary to the normal behaviour of layer-silicates, have a definite pore volume and no further uptake occurs when this is filled.

[1]  C. Breen,et al.  Mössbauer spectroscopic and thermogravimetric studies of tin-clay complexes , 1992, Clay Minerals.

[2]  C. Breen.  Thermogravimetric study of the desorption of cyclohexylamine and pyridine from an acid-treated Wyoming bentonite , 1991, Clay Minerals.

[3]  C. Breen.  Thermogravimetric and infrared study of the desorption of butylamine, cyclohexylamine and pyridine from Ni- and Co-exchanged montmorillonite , 1991, Clay Minerals.

[4]  D. Petridis,et al.  Pillaring of montmorillonite by organotin cationic complexes , 1989 .

[5]  A. Kostikas,et al.  Intercalation of dimethyltin(IV) cationic complexes in montmorillonite , 1988 .

[6]  J. M. Adams.  Synthetic Organic Chemistry Using Pillared, Cation‐Exchanged and Acid‐Treated Montmorillonite Catalysts ‐ a Review , 1988 .

[7]  J. M. Adams.  Synthetic organic chemistry using pillared, cation-exchanged and acid-treated montmorillonite catalysts — A review , 1987 .

[8]  C. Breen,et al.  The acidity of trivalent cation-exchanged montmorillonite. Temperature-Programmed desorption and infrared studies of pyridine and n-butylamine , 1987, Clay Minerals.

[9]  J. Ballantine.  The Reactions in Clays and Pillared Clays , 1986 .

[10]  I. W. Nowell,et al.  Organotin biocides: I. The structure of triphenyltin acetate , 1984 .

[11]  A. Newman,et al.  Water sorption on Ca-saturated clays: I. Multilayer sorption and microporosity in some illites , 1983, Clay Minerals.

[12]  D. W. Allen,et al.  A 119mSn Mössbauer study of the state of association of dibutyltin dichloride dispersed in PVC , 1983 .

[13]  J. Bellama,et al.  Organometals and Organometalloids: Occurrence and Fate in the Environment , 1979 .

[14]  R. S. Tobias.  The Chemistry of Organometallic Cations in Aqueous Media , 1979 .

[15]  T. Kelly,et al.  PREPARATION AND CATALYTIC PROPERTIES OF TIN ZEOLITES , 1978 .

[16]  A. Ritchie.  Chemical methods of silicate analysis , 1973 .

[17]  J. W. Ward.  A spectroscopic study of the surface of zeolite Y: the adsorption of pyridine , 1968 .

[18]  R. S. Tobias,et al.  Raman, Infrared, and Nuclear Magnetic Resonance Spectroscopic Studies on Aqueous Solutions of Dimethyltin(IV) Compounds: Structure and Bonding of the Aquodimethyltin Ion , 1964 .

[19]  R. S. Tobias,et al.  STUDIES ON THE SOLUBLE INTERMEDIATES IN THE HYDROLYSIS OF DIMETHYLTIN DICHLORIDE: EQUILIBRIUM CONSTANT FITTING WITH A HIGH SPEED DIGITAL COMPUTER , 1964 .

[20]  R. S. Tobias,et al.  Studies on the Mono- and Polynuclear Hydroxo Complexs of the Dimethyltin (IV) Ion in Aqueous Solution , 1962 .