A Molybdenum Trioxide Hybrid Decorated by 3-(1,2,4-Triazol-4-yl)adamantane-1-carboxylic Acid: A Promising Reaction-Induced Self-Separating (RISS) Catalyst.
A Molybdenum Trioxide Hybrid Decorated by 3-(1,2,4-Triazol-4-yl)adamantane-1-carboxylic Acid: A Promising Reaction-Induced Self-Separating (RISS) Catalyst.
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3-(1,2,4-三唑-4-基)金刚烷-1-甲酸修饰的三氧化钼杂化物：一种有前途的反应诱导自分离 (RISS) 催化剂
DOI：
10.1021/acs.inorgchem.9b02137
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发表时间：
2019
影响因子：
4.6
通讯作者：
I. S. Gonçalves
中科院分区：
文献类型：
--
作者：
A. B. Lysenko;G. A. Senchyk;K. V. Domasevitch;S. Henfling;O. Erhart;H. Krautscheid;P. Neves;A. A. Valente;M. Pillinger;I. S. Gonçalves
3-(1，2，4-三氮唑-4-基)金刚烷-1-羧酸(TradcH)是一种通过刚性的1，3-金刚烷二基间隔将羧酸和1，2，4-三唑基连接在一起的非双功能有机配体，用于合成MoVI氧化物有机杂化化合物。该配体从水中结晶为tradcH·H2O(1)，具有二维氢键网络，从乙醇中结晶为环状分子溶剂，组成为(TradcH)3·2EtOH(2)。在水热条件下用MoO_3处理tradcH得到了一种新的Mo_2O_3杂化产物[MoO_3(TradcH)]·H_2O(3)，并对其结构进行了表征。在化合物3中，钼原子形成由双三氮唑桥支撑的{μ_2-O-MoO_2}_n的聚合物锯齿链，而羧酸末端没有配位。Mo中心的配位环境为扭曲的顺式-{MoN2O4}八面体。杂化材料具有很高的热稳定性(高达270°C)，可用于较宽范围的催化氧化反应。它的催化行为可以比作可逆突变，具有均相催化和多相催化的优点。最初的固体物质转化为可溶的活性物种，后者在催化反应完成后恢复为原始材料，沉淀并允许直接分离/重复使用催化剂(就像多相催化剂)。该催化剂的化学反应范围包括亚硫氧化、氧化醇脱氢、醛氧化和烯烃环氧化，使用过氧化氢作为生态友好的氧化剂，产生水作为副产品。
3-(1,2,4-Triazol-4-yl)adamantane-1-carboxylic acid (tradcH), a heterobifunctional organic ligand in which carboxylic acid and 1,2,4-triazole groups are united through a rigid 1,3-adamantanediyl spacer, was employed for the synthesis of a MoVIoxide organic hybrid. The ligand crystallized from water as tradcH·H2O (1), possessing a two-dimensional hydrogen-bonding network, and from ethanol as a cyclic molecular solvate with the composition (tradcH)3·2EtOH (2). Treatment of tradcH with MoO3under hydrothermal conditions afforded a new Mo trioxide hybrid, [MoO3(tradcH)]·H2O (3), which was structurally characterized. In3, the molybdenum atoms form a polymeric zigzag chain of {μ2-O-MoO2}nwhich is supported by double triazole bridges, while the carboxylic acid termini are left uncoordinated. The coordination environment of the Mo centers appears as distortedcis-{MoN2O4} octahedra. The hybrid exhibits high thermal stability (up to 270 °C) and was employed for a relatively broad scope of catalytic oxidation reactions in the liquid phase. Its catalytic behavior may be compared to a reversible mutation, featuring the best sides of homogeneous and heterogeneous catalysis. The original solid material converts into soluble active species, and the latter revert to the original material upon completion of the catalytic reaction, precipitating and allowing straightforward catalyst separation/reuse (like a heterogeneous catalyst). This catalyst was explored for a chemical reaction scope covering sulfoxidation, oxidative alcohol dehydrogenation, aldehyde oxidation, and olefin epoxidation, using hydrogen peroxide as an eco-friendly oxidant that gives water as a coproduct.
三氧化钼杂化物设计中的三唑基、咪唑基和羧酸部分：光物理和催化行为
影响因子：
4.6
作者：
A. B. Lysenko;G. A. Senchyk;K. V. Domasevitch;M. Kobalz;H. Krautscheid;J. Cichos;M. Karbowiak;P. Neves;A. A. Valente;I. S. Gonçalves
通讯作者：
I. S. Gonçalves
用于二醇脱氧脱水生成烯烃的新型固体氧代铼和氧代钼催化剂
影响因子：
5.3
作者：
Sharkey, Bryan E.;Denning, Alana L.;Jentoft, Friederike C.;Gangadhara, Raju;Gopaladasu, Tirupathi V.;Nicholas, Kenneth M.
通讯作者：
Nicholas, Kenneth M.