N-Alkylation of tripodal iron(III) imidazolate complexes: Reactivity and structure |
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Authors: | Greg Brewer Cynthia Brewer Everett E. Carpenter Genevieve White |
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Affiliation: | a Department of Chemistry, The Catholic University of America, Washington, DC 20064, USA b Department of Chemistry, Howard University, Washington, DC 20059, USA c Department of Chemistry, Virginia Commonwealth University, Richmond, VA 23284-2006, USA |
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Abstract: | The N-alkylation of iron(III) complexes of the tripodal imidazolate complexes derived from the Schiff base condensation of tris(2-aminoethyl)amine (tren) with three molar equivalents of 2-imidazolecarboxaldehyde (2ImH), 4-imidazolecarboxaldehyde (4ImH) or 4-methyl-5-imidazolecarboxaldehyde (5-Me4ImH) was investigated. While each complex possesses three nucleophilic imidazolate nitrogen atoms, only the complex derived from 2-imidazolecarboxaldehyde, Fetren(2Im)3, was completely alkylated under the ambient conditions used in this work. Using methyl iodide as the alkylating agent, a correlation between spin state of the product and degree of methylation was observed. Low spin iron complexes were more nucleophilic than high spin systems. The structure reactivity relationship was exploited in the reaction of Fetren(2Im)3 with methyl iodide and allyl iodide to give [Fetren(N-Me2Im)3]2+ and [Fetren(N-allyl2Im)3]2+. The products are iron(II) due to reduction of the iron(III) by iodide ion which builds up in the reaction mixture as the alkylation reaction proceeds. These complexes were characterized by a number of methods including EA, IR, ES-MS, Mössbauer spectroscopy, magnetic susceptibility and X-ray diffraction. |
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Keywords: | Tripodal imidazolate complexes Iron complexes N-alkylation of coordinated imidazolate Mö ssbauer spectroscopy X-ray crystal structures |
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