Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
Inorg Chem. 2012 May 7;51(9):5224-34. doi: 10.1021/ic300123d. Epub 2012 Apr 6.
The facile aqueous medium reactions of copper(II) nitrate with BES biobuffer [(HOCH(2)CH(2))(2)N(CH(2)CH(2)SO(3)H), hereinafter referred as H(3)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(H(2)O)(4)][Cu(4)(μ(2)-Hbes)(4)(μ(2)-ba)]·H(2)O (1) and Cu(4)(μ(3)-Hbes)(4)(L){Li(H(2)O)(2)}·3nH(2)O {L = μ(2)-hba (2) and μ(2)-dhba (3)}. They were isolated as air-stable crystalline solids and fully characterized by infrared (IR) and UV-vis spectroscopy and electrospray ionization (ESI)-MS(±), elemental, thermal, and single-crystal X-ray diffraction analyses. The latter revealed that 1-3 have comparable packing patterns and unit cell parameters, being composed of similar Cu(4)(μ-Hbes)(4)(μ-carboxylate) cores and Li(H(2)O)(4) cations (in 1) or μ-Li(H(2)O)(2) groups (in 2 and 3), which are arranged into discrete 0D aggregates in 1 or infinite 3D noninterpenetrating metal-organic 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)(4(2).6)(2)(6(2).16(2).18(2)), 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 H(3)bes, 1-3 feature solubility in water and were applied as efficient and versatile catalyst precursors for the mild (60 °C) single-pot hydrocarboxylation, by CO and H(2)O, of various gaseous, linear, and cyclic C(n) (n = 2-9) alkanes into the corresponding C(n+1) carboxylic acids, in H(2)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-C bond formation reaction in aqueous acid-solvent-free medium.
硝酸铜(II)在 BES 生物缓冲液[(HOCH(2)CH(2))(2)N(CH(2)CH(2)SO(3)H)，以下简称 H(3)bes]存在下与各种苯羧酸[苯甲酸(Hba)、3-羟基苯甲酸(Hhba)和 3,5-二羟基苯甲酸(Hdhba)]在易处理的水介质中的反应，产生了三种新的异金属 Cu(II)/Li 材料的自组装生成，[Li(H(2)O)(4)][Cu(4)(μ(2)-Hbes)(4)(μ(2)-ba)]·H(2)O(1)和Cu(4)(μ(3)-Hbes)(4)(L){Li(H(2)O)(2)}·3nH(2)O {L = μ(2)-hba(2)和μ(2)-dhba(3)}。它们作为空气稳定的结晶固体被分离出来，并通过红外(IR)和紫外可见光谱以及电喷雾电离(ESI)-MS(±)、元素分析、热分析和单晶 X 射线衍射分析进行了充分的表征。后者表明，1-3 具有相似的堆积模式和单元胞参数，由类似的[Cu(4)(μ-Hbes)(4)(μ-羧酸根)]-核心和[Li(H(2)O)(4)]+(在 1 中)或[μ-Li(H(2)O)(2)]+(在 2 和 3 中)阳离子组成，它们在 1 中排列成离散的 0D 聚集体，在 2 和 3 中排列成无限的 3D 非穿插的金属有机网络。聚合物 2 和 3 的拓扑分析揭示了具有前所未有的拓扑结构的三节点 3,3,4-连接的基础网络，该拓扑结构由点符号(4.6.8)(4)(4(2).6)(2)(6(2).16(2).18(2))定义，进一步简化得到具有 binodal 4,4-连接网络的拓扑结构，拓扑结构符号为(PtS)。除了代表源自 H(3)bes 的配位化合物的非常罕见的例子外，1-3 在水中具有可溶性，并且作为温和(60°C)一锅法氢羧化的有效且多功能的催化剂前体，通过 CO 和 H(2)O 将各种气态、线性和环状 C(n)(n=2-9)烷烃转化为相应的 C(n+1)羧酸，在 H(2)O/MeCN 介质中和在过硫酸钾存在下在均相条件下进行。羧酸的总产率(基于烷烃)高达 78%，在温和条件下烷烃功能化领域是显著的，特别是在水相无酸溶剂中 C-C 键形成反应中。
