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 [(HOCHb>2b>CHb>2b>)b>2b>N(CHb>2b>CHb>2b>SOb>3b>H), hereinafter referred as Hb>3b>bes] 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(Hb>2b>O)b>4b>][Cub>4b>(渭b>2b>-Hbes)b>4b>(渭b>2b>-ba)]路Hb>2b>O (<b>1b>) and [Cub>4b>(渭b>3b>-Hbes)b>4b>(L){Li(Hb>2b>O)b>2b>}]b>nb>路3nHb>2b>O {L = 渭b>2b>-hba (<b>2b>) and 渭b>2b>-dhba (<b>3b>)}. 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 <b>1b>鈥?b>3b> have comparable packing patterns and unit cell parameters, being composed of similar [Cub>4b>(渭-Hbes)b>4b>(渭-carboxylate)]^{鈭?/sup> cores and [Li(Hb>2b>O)b>4b>]+ cations (in <b>1b>) or [渭-Li(Hb>2b>O)b>2b>]+ groups (in <b>2b> and <b>3b>), which are arranged into discrete 0D aggregates in <b>1b> or infinite 3D noninterpenetrating metal鈥搊rganic networks in <b>2b> and <b>3b>. The topological analysis of the coordination polymers <b>2b> and <b>3b> disclosed the trinodal 3,3,4-connected underlying nets with an unprecedented topology defined by the point symbol of (4.6.8)b>4b>(42.6)b>2b>(62.162.182), further simplification of which resulted in the binodal 4,4-connected nets with the <b>ptsb> (PtS) topology. Apart from representing very rare examples of coordination compounds derived from Hb>3b>bes, <b>1b>鈥?b>3b> 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 Hb>2b>O, of various gaseous, linear, and cyclic Cb>nb> (n = 2鈥?) alkanes into the corresponding Cb>n+1b> carboxylic acids, in Hb>2b>O/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.}