Theoretical Study and NBO Analysis of the Decomposition Kinetics of Oxetane, 2-Methyloxetane and 2,2-Dimethyloxetane

A theoretical study of the thermal decomposition kinetics of oxetane (1), 2-methyloxetane (2), and 2,2-dimethyloxetane (3) has been carried out at the B3LYP/6-311+G**, B3PW91/6-311+G**, and MPW1PW91/6-311+G** levels of theory. The MPW1PW91/6-311+G** method was found to give a reasonable good agreement with the experimental kinetics and thermodynamic parameters. The decomposition reaction of compounds 1～3 yields formaldehyde and the corresponding substituted olefin. Based on the optimized ground state geometries using MPW1PW91/6-311+G** method, the natural bond orbital (NBO) analysis of donor-acceptor (bond-antibond) interactions revealed that the stabilization energies associated with the electronic delocalization from σC3-C4 bonding to σ*O1-C2 antibonding orbitals decrease from compounds 1 to 3. The σC3-C4→σO1-C2 resonance energies for compounds 1～3 are 2.63, 2.59 and 2.45 kcal mol-1, respectively. Further, the results showed that the energy gaps between σC3-C4 bonding and σ*O1-C2 antibonding orbitals decrease from compounds 1 to 3. Also, the decomposition process in these compounds are controlled by σ→σ* resonance energies. Moreover, the obtained order of energy barriers could be explained by the number of electron-releasing methyl groups substituted to the Csp3 atom (which is attached to oxygen atom). NBO analysis shows that the occupancies of σCsp3-O bonds decrease for compounds 1～3 as 3<2<1, and those of σCsp3-O bonds increase in the opposite order (3 > 2 > 1). This fact illustrates a comparatively easier thermal decomposition of the sCsp3-O bond in compound 3 compared to compound 2, and in compound 2 compared to compound 1. NBO results indicate that these reactions are occurring through a concerted and asynchronous four-membered cyclic transition state type of mechanism.     

金催化剂上脂肪族硝基化合物与醛在氢气中选择还原耦合

采用TiO2上高度分散的金纳米粒子做催化剂，从脂肪族硝基化合物、醛和氢气可高选择性合成硝酮。与碳负载Pt催化剂相比，该催化体系上硝酮的选择性从50%增加到90%。其催化性能可有活性位结构、载体特性和反应条件精确调节。     

物理学咬文嚼字之三十六 Στοιχειαιο

Euclid的《几何原本》同化学术语中的化学计量比都来自希腊语Στοιχεια■ο,反映的是古希腊原子论的精神.     

NdxCo4Sb12化合物的快速合成及其热电性能研究

采用机械合金化和放电等离子烧结(MA-SPS)技术成功合成了NdxCo4Sb12化合物热电材料. 借助于先进的结构和性能表征手段, 系统研究了NdxCo4Sb12化合物成相和热电性能. 实验结果表明, NdxCo4Sb12化合物中稀土Nd的最佳添加量为x=1.0. Nd1.0Co4Sb12化合物具有较高的热电性能, 其中在400 ℃时具有最大ZT值0.265.     

杂氮三环类化合物的分子量测定

2,8,9-三氧杂-5-氮杂-1-M三环[3,3,3,0~(1,5)]十一碳烷,(?)(M=Si,B,Al,Ti),简称杂氮M三环。由于这类化合物具有特殊的分子结构及生物活性而受到人们的重视。作者报道过一系列杂氮三环类化合物的合成及结构测定,本文报道在非水介质中用酸碱滴定法     

辅酶B_(12)模型化合物研究 Ⅹ.Costa型模型化合物的合成、表征及电化学性质研究

合成了以 N,N′-双 (2 ,3-丁二酮 - 2 -亚胺 - 3-肟 )丙二胺为平面配体的烷基钴 Schiff碱一肟类 (Costa型 )模型化合物 [RCo(DO) (DOH) pn(H2 O) ] X,(R=n- C3 H7,n- C4H9,i- C4H9,n-C5H1 1 ,c- C6H1 1 ,CH2 C6H5.X=Cl O4-,PF-6)。用元素分析、紫外可见光谱和 1 H NMR进行了表征 ,并用循环伏安法研究了 [RCo(DO) (DOH) pn.H2 O] .Cl O4(R为上述六种烷基 )化合物的电化学性质 ,表明随烷基 R推电子能力增强 ,其氧化还原电位变负。     

钯类催化剂在形成碳－碳单键反应中的应用

钯催化反应是广泛被用于有机合成的简单而又重要的反应。主要综述钯类催化剂在形成碳－碳单键反应中的应用，着重阐述了卤代烃与有机金属化合物、烯烃、炔烃的交联反应。