A combined experimental and theoretical study of metallic salts of thiapentadienyl, sulfinylpentadienyl and butadienesulfonyls |
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Authors: | Prócoro Gamero-Melo Juvencio Robles M Angeles Paz-Sandoval |
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Institution: | a Departamento de Química, Centro de Investigación y de Estudios Avanzados del I.P.N., Apartado Postal 14-740, México D.F. 07000, Av. IPN # 2508, Col. San Pedro Zacatenco, D.F. 07360, Mexico b Facultad de Química, Universidad de Guanajuato, Col. Noria Alta S/N, Guanajuato 36050, Guanajuato, México |
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Abstract: | Alternative methods for the synthesis of the following acyclic salts (CH2CHCHCHS)M M = K, 1(K); Na, 1(Na); Li, 1(Li)], (CH2CHCHCHSO)M M = K, 2(K); Na, 2(Na)], (CH2CHCHCHSO2)M M = K, 3(K); Na, 3(Na); Li, 3(Li)], (CH(Me)CHC(Me)CHSO2)M Me5-syn, M = K, 9(K); Na, 9(Na); Li, 9(Li), (CH(Me)CHCHC(Me)S)M Me5-syn, M = K, 10(K); Na, 10(Na); Me5-anti, M = K, 11(K); Na, 11(Na)] are described, as a result of the activation of C-S bond in dihydrothiophenes by deprotonation with different bases. The effect of methyl substituents in the dihydrothiophenes is significant, which modifies considerably the choice of the base. The influence of the reaction conditions, type of solvent, base and dihydrothiophenes is analyzed. The NMR spectroscopy, including NOESY, ROESY and difference NOE establish the preferred U conformation for all derivatives, and support a delocalization of charge on the thiapentadienyl (1M) and sulfinylpentadienyl (2M) complexes. However, a conjugated diene structure is proposed on the butadienesulfonyl compounds (3M), in which the negative charge is delocalized in the SO2 fragment and stabilized with the corresponding cations (M = K, Na and Li). In presence of traces of base, compounds 3M suffer a rearrangement, to the most stable S conformer, 13M. The stability of 3M depends on the size of the cation, the greater the size, the greater stability. Furthermore, a theoretical study shows that electronic and geometrical properties (energy conformers, charge distributions and relative stabilities) of the thiapentadienyl, sulfinylpentadienyl and butadienesulfonyl anions and their corresponding metal salts 1M-3M (M = Li, Na and K) shows to be in good agreement with the experimental findings. |
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Keywords: | Heterodienes Anions Alkaline metals S O Ligands Thiapentadienyl |
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