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Interaction of Trialkyl Phosphites with Montmorillonites

Published online by Cambridge University Press:  28 February 2024

G. Dios Cancela ,
E. Romero Taboada ,
F. J. Huertas ,
A. Hernández Laguna  and
F. Sánchez Rasero
G. Dios Cancela
Affiliation:
Estación Experimental del Zaidín, Consejo Superior de Investigaciones Científicas Profesor Albareda, 1, 18008 Granada, Spain
E. Romero Taboada
Affiliation:
Estación Experimental del Zaidín, Consejo Superior de Investigaciones Científicas Profesor Albareda, 1, 18008 Granada, Spain
F. J. Huertas
Affiliation:
Estación Experimental del Zaidín, Consejo Superior de Investigaciones Científicas Profesor Albareda, 1, 18008 Granada, Spain
A. Hernández Laguna
Affiliation:
Estación Experimental del Zaidín, Consejo Superior de Investigaciones Científicas Profesor Albareda, 1, 18008 Granada, Spain
F. Sánchez Rasero
Affiliation:
Estación Experimental del Zaidín, Consejo Superior de Investigaciones Científicas Profesor Albareda, 1, 18008 Granada, Spain
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Abstract

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Complexes formed between montmorillonite, saturated in Li+, Na+, Mg2+, Ca2+, Co2+, Fe3+, Cu2+ and Zn2+, and trimethyl phosphites (TMP) and triethyl phosphites (TEP) were studied. In all of the cases, phosphites penetrate into the interlayer space of the montmorillonite and produce solvates whose basal spacing varies depending on the characteristics of the exchangeable cation. All the complexes with low basal spacing (Li+, Na+, Mg2+, Co2+ and Zn2+) are stable in vacuum, whereas those with high basal spacing, formed by the Ca2+ sample with TMP, and Ca2+ and Fe3+ samples with TEP are transformed into low basal spacing complexes in vacuum. The complexes with high basal spacing (Cu2+ sample with TMP and TEP) are stable in vacuum.

The TMP and TEP complexes stable in vacuum with low spacing are thermally destroyed in one or two stages with two loss maxima, as a result of partial burning of phosphite molecules. Those with high spacing (Cu2+) are destroyed in two stages; the first is probably the result of the transformation process from high to low spacing, as a consequence of the structural reorganization of the molecules which remain in the interlayer space, and the second, could be associated with the destruction of low spacing complexes.

The IR spectra show that the molecule and the cation are linked by the P of the phosphite, which produces a reinforcement of the other bonds in the molecule, caused by an inductive effect. The phosphite intercalation is accompanied by a partial isomerization of phosphite to phosphonate.

The heat of adsorption of phosphites shows that the molecule-cation bond is ion-dipole. In the Cu sample with trimethyl phosphite, this bond seems to be reinforced by retrodonation of electrons from copper to ligand. Finally, the possible disposition of phosphite molecules in the interlayer space is considered. For this purpose, ab initio calculations have been performed on the different conformers of the TMP molecule at 6–31G* and 6–31+G* basis sets.

Keywords

Ab initio CalculationsComplexesFormation MechanismMontmorilloniteStabilityTrialkyl Phosphites
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 2 , April 1996 , pp. 170 - 180
Copyright
Copyright © 1996, The Clay Minerals Society

References

Aroney, J., Chia, L.H.L., Le Febre, R.J.N. and Jaxby, J.D.L.. 1964. Molecular polarizability, dipole moments, molar Kerr constants, and conformations of eleven phosphates and phosphites triesters as solutes in benzene. J Chem Soc 2948.Google Scholar
Davidon, W.C. and Nazareth, L.. 1975. Program OC included with MONSTERGAUSS. The algorithm is described by Davidon W.C. Math Program 9: 1–30.CrossRefGoogle Scholar
Farzaneh, F. and Pinnavaia, T.J.. 1983. Metal complexes catalysts interlayered in smectite clay. Hydroformylation of 1-hexene with rhodium complexes ion-exchanged into hectorite. Inog Chem 22: 2216–2220.CrossRefGoogle Scholar
Levy, R. and Shainberg, I.. 1972. Calcium-magnesium exchange in montmorillonite and vermiculite. Clays & Clay Miner 20: 37–46.CrossRefGoogle Scholar
Norrish, K.. 1954. Swelling of montmorillonite. Diss Faraday Soc 18: 120–134.CrossRefGoogle Scholar
Peterson, M.R. and Poirier, R.A.. 1978. Program MONSTER-GAUSS. University of Toronto, Ontario (Canada).Google Scholar
Pinnavaia, T.J., Raythatha, R., Lee, J.G.S., Halloran, L.J. and Hoffman, J.F.. 1979. Intercalation of catalytically active metal complexes in mica-type silicates Rhodium hydrogenation catalysts. J Am Chem Soc 101: 6891–6897.CrossRefGoogle Scholar
Pinnavaia, T.J. and Welty, P.K.. 1975. Catalytic hydrogenation of 1-hexene by rhodium complexes in the intra-crystal space of a swelling layer lattice silicate. J Am Chem Soc 97: 3819–3820.CrossRefGoogle Scholar
Pinnavaia, T.J., Welty, P.K. and Hoffman, J.F.. 1976. Catalytic hydrogenation of unsaturated hydrocarbons by cationic rhodium complexes and rhodium metal intercalated in smectite. Proc Int Clay Conf Mexico. 1975 373–381.Google Scholar
Quayle, W.H. and Pinnavaia, T.J.. 1979. Utilization of a cationic ligand for the intercalation of catalytically active rhodium complexes in swelling layer-lattice silicates. Inorg Chem 18: 2840–2847.CrossRefGoogle Scholar
Raythatha, R. and Pinnavaia, T.J.. 1981. Hydrogenation of 1,3-butadienes with a rhodium-complexes-layered silicate intercalation catalyst. J Organomet Chem 218: 115–122.CrossRefGoogle Scholar
Raythatha, R.H. and Pinnavaia, T.J.. 1983. Clay intercalation catalysts interlayered with rhodium phosphine complexes. Surface effects on the hydrogenation and isomerization of 1-hexene. J Catal 80: 47–55.CrossRefGoogle Scholar
Schön, G. and Weiss, A.. 1970. Measurements of the dielectric properties of vermiculite simple crystals and interpretation of the high frequency conductivity within the zero, 155 and 255 states of hydratation. Reunion Hispano-Belga de Minerales de la Arcilla. Madrid. 37–44.Google Scholar
Thomas, L.E.. 1974. Interpretation of the infrared spectra of organophosphorus compounds. London: Hayden. 276p.Google Scholar
Van Asche, J.B., Van Canwelaert, F.H. and Uytterhoeven, J.B.. 1972. Sorption of organic polar gases on montmorillonite. Proc Int Clay Conf Madrid 1972. p. 605–615.Google Scholar
Vilkov, L.V., Akishin, P.A. and Salove, G.E.. 1965. Investigation electronographic of the structure of the molecules of P(OC2H5)3 and P(OC2H3)3 in phase gas. Ah Struk Khim 6: 355.Google Scholar