How to force a classical chelating ligand to a metal non-chelating bridge: the observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n
How to force a classical chelating ligand to a metal non-chelating bridge: the observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n
复制标题
如何迫使经典螯合配体形成金属非螯合桥：一维配合物{[Cu2(Piv)4(H3tBuDea)](Piv)}n中二乙醇胺罕见配位模式的观察
DOI：
10.1039/c3ce41657g
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发表时间：
2014
期刊：
影响因子：
3.1
通讯作者：
A. Pombeiro
中科院分区：
文献类型：
--
作者：
O. V. Nesterova;M. Kirillova;M. Silva;R. Boča;A. Pombeiro
通过硝酸铜(II)与新戊酸(HPiv)和N-叔丁基二乙醇胺(H2tBuDea)在乙腈溶液中的自组装反应制备了新型链配位聚合物{[Cu2(Piv)4(H3tBuDea)](Piv)}n (1)。晶体分析揭示了二乙醇胺配体1中极为罕见的非螯合桥配模式，这是首次在过渡金属配合物以及N原子上具有非配位脂肪族基团的二乙醇胺配合物中观察到。讨论了这种配位的可能原因，并分析了二乙醇胺基配体的主要配位模式。变温 (1.8–300 K) 磁化率测量表明，1 代表四羧酸二铜 (II) 的罕见例子，它在室温下是抗磁性固体。将此行为与文献示例进行比较，并在 DFT 计算的基础上进行讨论。此外，1 还可作为直链和环状 C5-C8 烷烃温和加氢羧化成相应羧酸的有效催化剂。
The novel chain coordination polymer {[Cu2(Piv)4(H3tBuDea)](Piv)}n (1) has been prepared through the self-assembly reaction of copper(II) nitrate with pivalic acid (HPiv) and N-tert-butyldiethanolamine (H2tBuDea) in acetonitrile solution. Crystallographic analysis revealed the extremely rare non-chelating bridging coordination mode of diethanolamine ligand in 1, observed for the first time in transition metal complexes, as well as in complexes of diethanolamine having a non-coordinating aliphatic group at the N atom. Possible reasons for such a coordination and analysis of the main coordination modes of diethanolamine-based ligands are discussed. Variable-temperature (1.8–300 K) magnetic susceptibility measurements showed that 1 represents a rare example of dicopper(II) tetracarboxylate that is a diamagnetic solid at room temperature. This behaviour is compared with literature examples and discussed on the basis of DFT calculations. Furthermore, 1 acts as an efficient catalyst for the mild hydrocarboxylation of linear and cyclic C5–C8 alkanes into the corresponding carboxylic acids.