Topologically Unique Heterometallic CuII/Li Coordination Polymers Self-Assembled from N,N-bis(2-Hydroxyethyl)-2-aminoethanesulfonic Acid Biobuffer: Versatile Catalyst Precurso

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• 作者：Marina V. Kirillova ; Alexander M. Kirillov ; Andr茅 N. C. Martins ; Claudia Graiff ; Antonio Tiripicchio ; Armando J. L. Pombeiro
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：May 7, 2012
• 年：2012
• 卷：51
• 期：9
• 页码：5224-5234
• 全文大小：573K
• 年卷期：v.51,no.9(May 7, 2012)
• ISSN：1520-510X

文摘

The facile aqueous medium reactions of copper(II) nitrate with BES biobuffer [(HOCH₂CH₂)₂N(CH₂CH₂SO₃H), hereinafter referred as H₃bes] in the presence of various benzenecarboxylic acids [benzoic (Hba), 3-hydroxybenzoic (Hhba), and 3,5-dihydroxybenzoic (Hdhba) acid] and lithium hydroxide gave rise to the self-assembly generation of three new heterometallic Cu^II/Li materials, [Li(H₂O)₄][Cu₄(渭₂-Hbes)₄(渭₂-ba)]路H₂O (1) and [Cu₄(渭₃-Hbes)₄(L){Li(H₂O)₂}]_n路3nH₂O {L = 渭₂-hba (2) and 渭₂-dhba (3)}. They were isolated as air-stable crystalline solids and fully characterized by infrared (IR) and UV鈥搗is spectroscopy and electrospray ionization (ESI)-MS(卤), elemental, thermal, and single-crystal X-ray diffraction analyses. The latter revealed that 1鈥?b>3 have comparable packing patterns and unit cell parameters, being composed of similar [Cu₄(渭-Hbes)₄(渭-carboxylate)]^{鈭?/sup> cores and [Li(H₂O)₄]+ cations (in 1) or [渭-Li(H₂O)₂]+ groups (in 2 and 3), which are arranged into discrete 0D aggregates in 1 or infinite 3D noninterpenetrating metal鈥搊rganic networks in 2 and 3. The topological analysis of the coordination polymers 2 and 3 disclosed the trinodal 3,3,4-connected underlying nets with an unprecedented topology defined by the point symbol of (4.6.8)₄(42.6)₂(62.162.182), further simplification of which resulted in the binodal 4,4-connected nets with the pts (PtS) topology. Apart from representing very rare examples of coordination compounds derived from H₃bes, 1鈥?b>3 feature solubility in water and were applied as efficient and versatile catalyst precursors for the mild (60 掳C) single-pot hydrocarboxylation, by CO and H₂O, of various gaseous, linear, and cyclic C_n (n = 2鈥?) alkanes into the corresponding C_n+1 carboxylic acids, in H₂O/MeCN medium under homogeneous conditions and in the presence of potassium peroxodisulfate. Total yields (based on alkane) of carboxylic acids up to 78% were achieved, which are remarkable in the field of alkane functionalization under mild conditions, especially for a C鈥揅 bond formation reaction in aqueous acid-solvent-free medium.}