Structural Study of Alkaline‐Earth Metal Heterocycles Supported by Triazole‐based Sulfur Ligands |
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Authors: | Jhon A Balanta‐Díaz Mónica Moya‐Cabrera Vojtech Jancik Rubén A Toscano T Jesús Morales‐Juárez Dr Raymundo Cea‐Olivares |
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Institution: | 1. Instituto de Química, Universidad Nacional Autónoma de México Circuito Exterior s/n, Ciudad Universitaria, México D.F. 04510, México;2. Centro Conjunto de Investigación en Química Sustentable UAEM‐UNAM, Carr. Toluca‐Atlacomulco Km 14.5, Toluca, Estado de México, 50200, México;3. Facultad de Química, Universidad Autónoma del Estado de México, Paseo Tollocan y Colón, 50120, Toluca, Estado de México, México |
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Abstract: | The alkaline earth metal complex Mg{4,5‐(P(S)Ph2)2}2tz}2(thf)4] ( 2 ) and the bimetallic complexes, M{4,5‐(P(S)Ph2)2}2tz}2(thf)]2 M = Ca ( 3 ), Sr ( 4 ), Ba ( 5 )], SrI{4,5‐(P(S)Ph2)2tz}2(thf)3]2 ( 6 ), and {BaI(4,5‐(P(S)Ph2)2tz)}2(thf)7] ( 7 ) were prepared in good yields from the metathesis reactions of the potassium salt of 4,5‐bis(diphenylthiophosphoranyl)‐1,2,3‐triazole H{4,5‐(P(S)Ph2)2tz}] ( 1 ) and MI2 (M = Ca, Sr, Ba), whereas the tetrametallic magnesium hydroxide Mg2(μ‐OH){4,5‐(P(S)Ph2)2}2tz}3]2 ( 8 ) was obtained as the hydrolysis product from the starting material (MgnBuCl) and 1 . The NMR study of 2 – 8 in solution suggests the formation of solvated species in CD3OD‐d4, whereas for 4 , 5 , and 6 a fluxional behavior is observed in CD2Cl2. The structural analyses of 3 – 5 , 6 , and 7 in solid state reveal in all cases a central core defined by M2N4 heterocycle bearing M–S bonding. The degree of aggregation observed for these compounds depends significantly on the size of the metal atom as well as on the metal‐ligand molar ratio employed for each reaction. |
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Keywords: | Alkaline earth metals Chalcogens S ligands Metathesis reactions NMR spectroscopy |
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