Spectroscopic study in the UV-Vis, near and mid IR of cationic species formed by interaction of thiophene, dithiophene and terthiophene with the zeolite H-Y

被引:51
作者
Geobaldo, F
Palomino, GT
Bordiga, S
Zecchina, A
Areán, CO
机构
[1] Politecn Torino, Dipartimento Sci Mat & Ingn Chim, I-10129 Turin, Italy
[2] Univ Turin, Dipartimento Chim Inorgan Chim Fis & Chim Mat, I-10125 Turin, Italy
[3] Univ Balearic Isl, Dept Quim, E-07071 Palma de Mallorca, Spain
关键词
D O I
10.1039/a807353h
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The vibrational (in the mid-IR and near-IR) and the UV-Vis spectra of products formed upon interaction of thiophene with H-Y, show the initial formation of neutral hydrogen bonded adducts. In the presence of thiophene excess, protonation slowly occurs with formation of C(4)H(5)S(+) followed by oligomerization leading to C(8)H(7)S(2)(+), C(12)H(9)S(3)(+) and more complex species. This conclusion is fully confirmed by the study of the direct interaction of H-Y with dithiophene and terthiophene, where protonated C(8)H(7)S(2)(+) and C(12)H(9)S(3)(+) are produced in the initial interaction stages. The ascertained occurrence of intramolecular and intermolecular hydrogen transfer points towards a network of complex reactions leading to the final formation of some families of similar isomers. Some of the protonated (oligomeric) species interact via strong hydrogen bonds with the unreacted Bronsted groups of H-Y. The positively charged species can easily react with NH, with the formation of NH(4)(+) and neutral species. At room temperature the process is partially reversible.
引用
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页码:561 / 569
页数:9
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