Tri-Organotin(IV) Coordination Compounds Derived from a Cholesteryl Dithiophosphonate Ligand. Synthesis, Characterization, Structure, and Antibacterial Evaluation
DOI:
https://doi.org/10.29356/jmcs.v70i1.2489Keywords:
Dithiophosphonates, cholesteryl complexes, organotin, X-ray single crystal, complex biological activityAbstract
Among the dithio-organophosphorus metal coordination compounds, dithiophosphonates have received significantly less attention than dithiophosphates and dithiophosphinates. This is partly due to the inherent difficulties in synthesizing phosphonates. Herein, we report the synthesis and characterization of four new organotin(IV) dithiophosphonate coordination compounds, bearing an O-cholesteryl substituent on phosphorus: [Me3Sn{S2P(O-cholesteryl)(4-MeOC6H4)}] (2), [Bu3Sn{S2P(O-cholesteryl)(4-MeOC6H4)}] (3), [Cy3Sn{S2P(O-cholesteryl)(4-MeOC6H4)}] (4), [Ph3Sn{S2P(O-cholesteryl)(4-MeOC6H4)}] (5). These compounds were obtained through the reaction between the triethylammonium salt of O-3-b-cholest-5-en-3-yl)(4-methoxyphenyl)dithiophosphonate (1) and the corresponding triorganotin(IV) chlorides. The compounds were characterized using elemental analysis, IR spectroscopy, and NMR spectroscopy (1H, 13C, 31P, and 119Sn). Infrared spectra (solid-state) suggest that the Sn(IV) is coordinated in an anisobidentate mode. In solution, the 119Sn NMR chemical shifts indicate tetracoordination for 2 and 4 and pentacoordination for 3 and 5. Single-crystal X-ray analysis of 5 revealed an anisobidentate coordination mode of the dithiophosphonate and a highly distorted trigonal bipyramidal geometry around Sn(IV), closer to a trigonal bipyramid than to a square pyramid. The phosphorus atom is chiral and adopts the relative configuration R. The antibacterial test indicates that compound 5 exhibits antibacterial activity, while the others show no inhibition against any of the bacterial strains used.
Resumen. Dentro de los compuestos metálicos de coordinación conteniendo ligantes ditio-organofosforados, los ditiofosfonatos han recibido significativamente mucha menos atención que los bien estudiados ditiofosfinatos y ditiofosfatos. Lo anterior es parcialmente debido a las inherentes mayores dificultades sintéticas de los ditiofosfonatos. En esta investigación informamos la síntesis y caracterización de cuatro nuevos compuestos de coordinación de organoestaño(IV) con un ligante ditiofosfonato, conteniendo O-colesterilo. Los compuestos de organoestaño (IV) sintetizados son: [Me3Sn{S2P(O-colesteril)(4-MeOC6H4)}] (2), [Bu3Sn{S2P(O-colesteril)(4-MeOC6H4)}] (3), [Cy3Sn{S2P(O-colesteril)(4-MeOC6H4)}] (4), [Ph3Sn{S2P(O-colesteril)(4-MeOC6H4)}] (5). La síntesis se llevó a cabo a través de la reacción entre la sal de trietilamonio del O-3-b-colest-5-en-3-yl)(4-metoxifenil)ditiofosfonato (1) y los correspondientes cloruros de triorganoestaño(IV). Los compuestos obtenidos fueron caracterizados por análisis elemental, espectroscopia IR y RNM (1H, 13C, 31P, y 119Sn). Los espectros infrarrojos (estado sólido) sugieren que el Sn(IV) se encuentra coordinado al ligante en un modo anisobidentado, mientras que en solución los desplazamientos químicos de 119Sn RNM indican tetracoordinación para 2 y 4 y pentacoordinación para 3 y 5. El análisis por rayos X de monocristal de 5 revela un modo de coordinación anisobidentado del ditiofosfonato y una geometría trigonal bipiramidal altamente distorsionada alrededor del Sn(IV), la cual es más cercana a una bipirámide trigonal que a una pirámide cuadrada, donde el átomo de fósforo es quiral y asume la configuración relativa R. Las pruebas antibacterianas indican que el compuesto 5 exhibe actividad antibacteriana, mientras que los demás no muestran inhibición contra ninguna de las cepas utilizadas.
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Copyright (c) 2026 Perla Román-Bravo, Gabriela Vargas-Pineda, Fernando Carvajal-Román, Marcela López-Cardoso, Macdiel Acevedo-Quiroz, Patricia Alvarez-Fitz, Raymundo Cea Olivares
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