Synthesis and Reactivity of Mononuclear Iron Models of [Fe]‐Hydrogenase that Contain an Acylmethylpyridinol Ligand

[Fe]‐hydrogenase has a single iron‐containing active site that features an acylmethylpyridinol ligand. This unique ligand environment had yet to be reproduced in synthetic models; however the synthesis and reactivity of a new class of small molecule mimics of [Fe]‐hydrogenase in which a mono‐iron center is ligated by an acylmethylpyridinol ligand has now been achieved. Key to the preparation of these model compounds is the successful C?O cleavage of an alkyl ether moiety to form the desired pyridinol ligand. Reaction of solvated complex [(2‐CH₂CO‐6‐HOC₅H₃N)Fe(CO)₂(CH₃CN)₂]⁺(BF₄)^? with thiols or thiophenols in the presence of NEt₃ yielded 5‐coordinate iron thiolate complexes. Further derivation produced complexes [(2‐CH₂CO‐6‐HOC₅H₃N)Fe(CO)₂(SCH₂CH₂OH)] and [(2‐CH₂CO‐6‐HOC₅H₃N)Fe(CO)₂(CH₃COO)], which can be regarded as models of FeGP cofactors of [Fe]‐hydrogenase extracted by 2‐mercaptoethanol and acetic acid, respectively. When the derivative complexes were treated with HBF₄?Et₂O, the solvated complex was regenerated by protonation of the thiolate ligands. The reactivity of several models with CO, isocyanide, cyanide, and H₂ was also investigated.     

基于Khimera软件的Se和Sn氧化动力学参数计算

反应速率常数和指前因子、活化能等动力学参数的准确性是研究痕量元素动力学模型的关键,在Se和Sn氧化过程的反应机理研究基础上,借助于量化软件Gaussview和Gaussian及动力学软件Khimera,采用量子化学从头计算理论对Se和Sn氧化过程进行研究,最终得到了在200~2000K温度区间内的反应速率k随温度T变化的关系,进一步计算了Arrhenius参数,得出了活化能随温度变化的关系,弥补了以往只能计算单个温度点的化学反应速率值的不足,为深入研究煤燃烧过程中Se和Sn的生成与排放的动力学模型提供了依据。     

Organocatalytic Control over a Fuel-Driven Transient-Esterification Network**

Signal transduction in living systems is the conversion of information into a chemical change, and is the principal process by which cells communicate. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. However, man-made catalytically controlled networks are rare. We incorporated catalysis into an artificial fuel-driven out-of-equilibrium CRN, where the forward (ester formation) and backward (ester hydrolysis) reactions are controlled by varying the ratio of two organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. This fuel-driven strategy was expanded to a responsive polymer system, where transient polymer conformation and aggregation are controlled through fuel and catalyst levels. Altogether, we show that organocatalysis can be used to control a man-made fuel-driven system and induce a change in a macromolecular superstructure, as in natural non-equilibrium systems.     

碱活化多孔碳用于分离甲苯及活化/吸附机理

采用生物质木质素磺酸钠(SLS)为碳源, 先与硬模板NaCl混合预碳化, 再加入活化剂NaOH在氮气保护下升温至850 ℃碳化, 得到SLS基碱活化的多孔碳吸附剂(SPCN). 将SPCN用于吸附液体石蜡中芳香烃甲苯, 对比研究了不同活化剂加入量对SPCN结构、 性质及吸附效果的影响. 结果表明, SPCN表面具有丰富的官能团和发达的微/介孔结构, 活化剂加入量对比表面积的影响为先增大后减小, 碱/碳质量比为1∶1时比表面积达到最大值(710.4 m ²/g); 吸附量与比表面积呈正相关, 样品SPCN-1的最大吸附量为2875.17 mg/g, 远高于商业吸附剂, 经5次吸附-解吸循环后仍保持92.5%的吸附效率. 探究了活化机理, NaOH、 碳质和气体发生氧化还原反应释放气体留下孔隙, 经充分酸洗、 水洗后得到永久孔道. 最后, 结合扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 拉曼光谱(Raman)、 X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)和比表面积分析等结果证明了吸附机理主要是孔隙填充效应、 范德华力、 π-π相互作用及电子供/受体作用的共同作用. 首次报道了SPCN应用的新方向并探究了活化与吸附机理, 制备方法简易、 经济, 产品循环稳定性好、 无污染, 有望用于工业化生产.     

NN型双齿半夹心Ru(Ⅱ)化合物:无受体脱氢环化合成喹啉和吡咯衍生物的催化剂

四个含NN型双齿配体的半夹心(η^6-p-cymene)Ru(II)化合物被成功制备.这四个化合物分别为(η^6-p-cymene)-Ru(C5H4N-C5H3N-OH)(1),(η^6-p-cymene)Ru(C5H4N-CH2-C5H4N)(2),(η^6-p-cymene)Ru(C5H4N-CH2-C5H3N-OH)(3)和(η^6-p-cymene)Ru(C5H4N-CH2-C5H3N-OCH3)(4).这些化合物通过核磁氢谱、碳谱和元素分析等手段表征,化合物2的结构被X射线单晶衍射证实.将这些化合物应用于催化氨醇与酮的环化反应,其中3的催化效率最高.在0.5mol%化合物3的存在下,制备了一系列喹啉和吡啶衍生物.     

铜催化的α-氨基丙二腈的脱氰氧代反应：一种合成叔酰胺的新方法

新反应、新试剂的发展是有机合成化学的重要研究内容,基于前期在α-氨基丙二腈合成方法学方面的工作基础,我们发展了一例铜催化的α-氨基丙二腈的脱氰氧代反应.通过将甲酰胺转化为α-氨基丙二腈后,借助其亲核属性来合成α-氨基丙二腈底物,而后将底物重新转化为酰胺,从而实现形式上的氨基甲酰负离子的亲核加成（取代）反应.该工作首次完成了形式上的甲酰胺碳原子的极性反转,实现了将α-氨基丙二腈作为氨基甲酰负离子替代物的反应新模式,为叔酰胺化合物的合成提供了新的思路和方法,且具有反应条件简单,底物适用性广及适合克级规模制备等特点.     

Impact of Positional Isomerism on Pathway Complexity in Aqueous Media

Pathway complexity has become an important topic in recent years due to its relevance in the optimization of molecular assembly processes, which typically require precise sample preparation protocols. Alternatively, competing aggregation pathways can be controlled by molecular design, which primarily rely on geometrical changes of the building blocks. However, understanding how to control pathway complexity by molecular design remains elusive and new approaches are needed. Herein, we exploit positional isomerism as a new molecular design strategy for pathway control in aqueous self‐assembly. We compare the self‐assembly of two carboxyl‐functionalized amphiphilic BODIPY dyes that solely differ in the relative position of functional groups. Placement of the carboxyl group at the 2‐position enables efficient pairwise H‐bonding interactions into a single thermodynamic species, whereas meso‐substitution induces pathway complexity due to competing hydrophobic and hydrogen bonding interactions. Our results show the importance of positional engineering for pathway control in aqueous self‐assembly.     

Synergistic N‐Heterocyclic Carbene/Palladium‐Catalyzed Umpolung 1,4‐Addition of Aryl Iodides to Enals

An umpolung 1,4‐addition of aryl iodides to enals promoted by cooperative (terpy)Pd/NHC catalysis was developed that generates various bioactive β,β‐diaryl propanoate derivatives. This system is not only the first reported palladium‐catalyzed arylation of NHC‐bound homoenolates but also expands the scope of NHC‐induced umpolung transformations. A diverse array of functional groups such as esters, nitriles, alcohols, and heterocycles are tolerated under the mild conditions. This method also circumvents the use of moisture‐sensitive organometallic reagents.     

Palladium-catalyzed regioselective cascade reaction of carbon dioxide,amines and allenes for the synthesis of functionalized carbamates

A palladium-catalyzed regioselective three-component cascade reaction of carbon dioxide,amines and allenes has been developed,providing an expedient and practical method for the construction of a range of functionalized carbamates containing dihydrobenzofuran or indole moiety in moderate to excellent yields.The broad substrate scope,good functional group tolerance and excellent chemo-and regioselectivity are the features of the transformation.     

Finite-time stability of Hadamard fractional differential equations in weighted Banach spaces

Nonlinear Dynamics - The main purpose of this paper is to investigate the finite-time stability of Hadamard fractional differential equations (HFDEs). Firstly, the standard definitions of...