Diazotization of the Amino Acid [closo-1-CB9H8-1-COOH-6-NH3] and Reactivity of the [closo-1-CB9H8-1-COO-6-N2]鈭?/sup

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• 作者：Bryan Ringstrand ; Piotr Kaszynski ; Victor G. Young ; Jr.
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：March 21, 2011
• 年：2011
• 卷：50
• 期：6
• 页码：2654-2660
• 全文大小：982K
• 年卷期：v.50,no.6(March 21, 2011)
• ISSN：1520-510X

文摘

A comparative study of the reactivity of dinitrogen acids [closo-1-CB₉H₈-1-COOH-10-N₂] (3[10]) and [closo-1-CB₉H₈-1-COOH-6-N₂] (3[6]) was conducted by diazotization of a mixture of amino acids [closo-1-CB₉H₈-1-COOH-6-NH₃] (1[6]) and [closo-1-CB₉H₈-1-COOH-10-NH₃] (1[10]) with NO⁺BF₄^{鈭?/sup> in the presence of a heterocyclic base (pyridine, 4-methoxypyridine, 2-picoline, or quinoline). The 10-amino acid 1[10] formed an isolable stable 10-dinitrogen acid 3[10], while the 6-dinitrogen carboxylate 3[6]鈭?/b> reacted in situ, giving products of N-substitution at the B6 position with the heterocyclic solvent (4[6]). The molecular and crystal structures for pyridinium acid 4[6]a were determined by X-ray crystallography. The electronic structures and reactivity of the 6-dinitrogen derivatives of the {1-CB₉} cluster were assessed computationally at the B3LYP/6-31G(d,p) and MP2/6-31G(d,p) levels of theory and compared to those of the 10-dinitrogen, 2-dinitrogen, and 1-dinitrogen analogues.}