Ligand-modification effects on the reactivity, solubility, and stability of organometallic tantalum complexes in water |
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Authors: | Conde Ana Fandos Rosa Hernández Carolina Otero Antonio Rodríguez Ana Ruiz María José |
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Institution: | Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, Instituto de Nanociencia, Nanotecnología y Materiales Moleculares (INAMOL), Facultad de Ciencias del Medio Ambiente, Avda. Carlos III, s/n, 45071 Toledo, Spain. |
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Abstract: | Tantalum complexes TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NMe(2))=CH)py}] (4) and TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NH(2))=CH)py}] (5), which contain modified alkoxide pincer ligands, were synthesized from the reactions of TaCp*Me{κ(3)-N,O,O-(OCH(2))(OCH)py}] (Cp* = η(5)-C(5)Me(5)) with HC≡CCH(2)NMe(2) and HC≡CCH(2)NH(2), respectively. The reactions of TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(Ph)=CH)py}] (2) and TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(SiMe(3))=CH)py}] (3) with triflic acid (1:2 molar ratio) rendered the corresponding bis-triflate derivatives TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(Ph)=CH(2))py}] (6) and TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(SiMe(3))=CH(2))py}] (7), respectively. Complex 4 reacted with triflic acid in a 1:2 molar ratio to selectively yield the water-soluble cationic complex TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH)py}]OTf (8). Compound 8 reacted with water to afford the hydrolyzed complex TaCp*(OH)(H(2)O){κ(3)-N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH(2))py}](OTf)(2) (9). Protonation of compound 8 with triflic acid gave the new tantalum compound TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH)py}](OTf)(2) (10), which afforded the corresponding protonolysis derivative TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH(2))py}](OTf) (11) in solution. Complex 8 reacted with CNtBu and potassium 2-isocyanoacetate to give the corresponding iminoacyl derivatives 12 and 13, respectively. The molecular structures of complexes 5, 7, and 10 were established by single-crystal X-ray diffraction studies. |
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