(CH2)2N和(CH3)2NH+的密度泛函理论计算

用密度泛函理论UB3LYP／6-31G（d,p）方法研究了二甲胺自由基（CH3）2N及其质子化离子（CH3）2NH 的构象和超精细结构．在由构象研究得到的两种自由基的最稳定结构上,用密度泛函的UB3LYP和UB3PW91方法及从头计算的UHF、UMP2（FULL）方法计算了α-质子、β-质子和N核上的超精细偶合常数A（Hα）、A（Hβ）和A（N）结果表明：两种自由基中甲基内旋转的位垒均很低,分别为0．46kJ·mol-1（（CH3）2NH ）和2．6kJ·mol-1（（CH3）2N）．UB3LYP／6-31G（d,p）和UB3PW91／6-31G（d,p）计算的A（Hα）、A（Hβ）和A（N）与ESR实验结果符合得很好,UMP2／6-31G（d,p）方法的计算值与实验值符合得也较好．     

The reaction of Sn[CH(SiMe3)2]2 with ethyne: formation of (HCC)Sn[CH(SiMe3)2]2(μ-trans-CHCH)Sn[CH-(SiMe3)2]2(CHCH2)

The reaction of Sn[CH(SiMe₃)₂]₂ and ethyne at ambient temperature affords a mixture of products, from which the title compound has been separated and identified by IR, ¹H, and ¹³C NMR spectroscopy.     

Intramolecular Rearrangements of >Si(O–C·=O)(CH2–CH3) and >Si(CH2–CH·–CH3)(CH2–CH3) Radicals

Using ESR and IR spectroscopy, the structures of >Si(O–C^·=O)(CH₂–CH₃) (1) and >Si(CH₂–CH^·–CH₃)(CH₂–CH₃) (2) radicals were deciphered. The directions and kinetic parameters of reactions of intramolecular rearrangements in these radicals were determined. The reactions of hydrogen atom abstraction in radical (1) from the CH₂ and CH₃ groups were studied. It was found that the endothermic reaction of hydrogen atom abstraction from the methyl group occurs at a higher rate than the exothermic reaction with the methylene group. The differences are determined by changes in the size of a cyclic transition state. Based on the experimental data, the strengths of separate C–H bonds in surface fragments are compared. The rearrangement >Si(CH₂–CH^·–CH₃)(CH₂–CH₃) >Si(C^·(CH₃)₂)(CH₂–CH₃) was discovered and its mechanism was determined. One of its steps is the skeletal isomerization Si- (2)- _. (1)Si- (1)- _. (2). Experimental data are analyzed using the results of quantum-chemical calculations of model systems.     

[ZnN(CH2CH2NH2)2(CH2CH2N=CHC6H4O)]·Pic的合成与晶体结构

在不加任何碱的条件下,三[2-(亚水杨基胺)乙基]胺与苦味酸锌[Zn(Pic)26H2O]在乙醇中反应,得到了较为少见的多胺单缩合西夫碱配体的配合物[ZnN(CH2CH2NH2)2(CH2CH2N=CH-C6H4O)]Pic。化学式为C19H23N7O8Zn,Mr=542.81,晶体属三斜晶系,空间群为P,晶胞参数为a=0.7494(3),b=1.1917(5),c=1.3142(6)nm,a=78.111(7),b=79.093(7),g=78.577(7),V=1.1121(8)nm3,Dc=1.621g/cm3,m(MoKa)=1.167mm-1,Z=2,F(000)=560,在1.602s(I)的可观测点为2433个,最终偏离因子R=0.0555,wR=0.1139。配合物中Zn(II)与配体的4个N原子和1个O原子配位形成变形的三角双锥结构,桥头N和O为锥顶,4个配位N中桥头N与金属离子的配位作用最弱。晶体通过p-p堆积和分子内、分子间的氢键作用形成二维层状超分子结构。     

[C5H4C(CH3)2CH2CH=CH2]Sm(OH)Cl·2MgCl2·4THF的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了［Ｃ５Ｈ４Ｃ（ＣＨ３）２ＣＨ２ＣＨ＝ＣＨ２］Ｓｍ（ＯＨ）Ｃｌ·２ＭｇＣｌ２·４ＴＨＦ的晶体结构。它属三斜晶系,空间群为Ｐ＾－１,ａ＝１０．７７３（２）,ｂ＝１２．８３６（３）,ｃ＝１５．４７８（３）Ａ,ａ＝１１１．４６（３）,β＝１０７．７１（３）,γ＝９２．５４（３）°,Ｖ＝１８６８（１）Ａ＾３,Ｍｒ＝８２７．９１,Ｄｘ＝１．４７２ｇ／ｃｍ＾３,μ＝２．０００６ｍｍ     

(CH2)2O, (CH2)2S与双卤分子间卤键的理论研究

运用量子化学密度泛函B3LYP方法, 采用6-311＋＋G(d,p)及aug-cc-pVDZ基组, 通过CP校正的几何梯度优化对(CH2)2O和(CH2)2S与双卤分子XY (XY＝Cl2, Br2, ClF, BrF, BrCl)形成的卤键复合物的几何构型、振动频率和相互作用能等进行了研究. 利用电子密度拓扑分析理论方法对卤键复合物的拓扑性质进行了分析研究, 探讨了该类分子间卤键的作用本质. 结果表明, (CH2)2O和(CH2)2S与双卤分子间的卤键介于共价键与离子键之间, 偏于静电作用成分为主. 形成卤键后, 双卤分子的键长增加, 振动频率减小, 原子积分性质发生改变. 卤键键长的变化、键能的强弱、键鞍点处的电子密度值与双卤分子的电负性有关.     

Cluster Complexes of Polythioether Macrocycles: The Synthesis and Molecular Structures of Ru6(CO)13(cis-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C) and Ru6(CO)13(trans-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C)

The reaction of a mixture of cis-3,7,11-trimethyl-1,5,9-trithiacyclododecane, cis-Me₃12S3, 1 and trans-3,7,11-trimethyl-l,5,9-trithiacyclododecane, trans-Me₃12S3, 2, with Ru₆(CO)₁₇(μ ₆-C), 3, yielded three new cluster compounds Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 4, and two isomers of Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 5a and 5b. The molecular structures of 4 and 5b were established by single crystal X-ray diffraction analyses. In both complexes, the macrocycles have adopted tridentate coordination with one of the sulfur atoms in a bridging position. Two carbonyl ligands occupy bridging positions in each compound. Crystal Data for 4·Me₂CO: space group=P2₁/n, a=11.295(1) Å, b=17.547(3) Å, c=20.318(3) Å, β=93.71(1)°, Z=4, 2900 reflections, R=0.025. Crystal Data for 5b·1.5 C₆H₆: space group=Pbca, a=31.8900(8) Å, b=23.4330(6) Å, c=21.6240(4) Å, Z=16, 12163 reflections, R=0.040.     

过渡金属双核化合物Cr_2(O_2CH)_4、Mo_2(O_2CH)_4及CrMo(O_2CH)_4的从头计算研究

用从头计算方法研究双核过渡金属化合物Cr_2(O_2CH)_4、MO_2(O_2CH)_4及CrMo(O_2CH)_4的金属—金属多重键性质,计算优化键长与实验值符合很好,原子布居表明Mo_2(O_2CH)_4和CrMo(O_2CH)_4中Mo—Mo、Cr—Mo键分别为σ~2π~4δ~2与σ~2δ~2π~4四重键,同时金属-d与氧和碳-p电子间的电荷重叠对分子稳定有相当贡献。对Cr_2(O_2CH)_4在优化键长下3种组态σ~2δ~2δ~(*2)σ~(*2)、π~4π~(*4)及σ~2δ~2π~4的电子结构、原子布居、总能量及电离能的计算进行比较,讨论了Cr—Cr的成键性质,指出描述Cr—Cr间金属多重键本质必须考虑电子相关效应的影响。     

Preparation and structural characterization of the hexatungsten cluster complex (EDTEH)2[W6(μ3-Cl)8Cl6], (EDTEH=(MeO2CCH2)2N(H)CH2CH2N(CH2CO2Me)2+

The hexanuclear tungsten cluster complex [W₆(₃-Cl)₈Cl₆]^2–,1 was isolated as a salt of the cation (MeO₂CCH₂)₂N(H)CH₂CH₂N(CH₂CO₂Me)₂₊, EDTEH⁺, by crystallization from methanol solvent of the product obtained from the reaction of (H₃O)₂[W₆(₃-Cl)₈Cl₃] with the disodium salt of ethylenediaminetetraacetic acid. The compound was charcterized by single-crystal X-ray diffraction analysis. The cluster anion contains an octahedral arrangement of six tungsten atoms with chloride ligands bridging the eight triangular faces of the cluster and one chloride ligand terminally coordinated to each of the six tungsten atoms. The cation (EDTEH)⁺ achieves its positive charge by protonation of one of the nitrogen atoms. Crystal data: space group = P2₁/a,a=10.689(2) Å,b=22.931(6) Å,c=12.093(3) Å, =98.41(2)°,Z=2, 2476 reflections,R=0.028.     

二维配位聚合物(NH3+CH2CH2NH3+)(NH2CH2CH2NH3+)2[(VO)4(PO4)4(H2O)2]·2H2O的水热合成及晶体结构

无机-有机杂化钒氧酸盐由于其结构的多样性以及在催化、医药、光、电、磁等材料领域中的应用前景而受到人们的广泛关注。近年来这一研究领域的重大进步是将有机氮配体或者过渡金属配合物直接连接到矾氧骨架上以获得各种新奇结构。合成出许多属于L/V/O、MXLY/V/O、L/P/V/O和MXLY     

Synthesis and Structure of Acetonitrile Solvates of Copper(II) Monofluoroacetate and Silver(I) Trifluoroacetate, [Cu2(CH2FCOO)4· 2CH3CN](CH3CN) and Ag3(CF3COO)3(CH3CN)2

Compounds [Cu₂(CH₂FCOO)₄· 2CH₃CN](CH₃CN) (I) and Ag₃(CF₃COO)₃(CH₃CN)₂(II) were synthesized and studied by X-ray structural analysis. Crystals Iare monoclinic, space group C2/c, a= 27.854(6), b= 8.286(2), c= 19.428(4) Å, = 106.82(3)°, V= 4292(2) ų, Z= 8, R ₁= 0.0426; crystals IIare triclinic, space group , a= 8.676(2), b= 9.819(2), c= 11.961(2) Å, = 95.27(3), = 109.59(3)°, = 104.60(3)°, V= 911.4(3) ų, Z= 2, R ₁= 0.0252. Structure Iis composed of the structural units (lanterns) typical of copper(II) carboxylates. The presence of an additional acetonitrile molecule noncoordinated by the copper atoms makes it possible to consider compound Ias a lattice clathrate. Structure IIhas no analogs among the silver carboxylates. It simultaneously contains silver atoms with coordination numbers varying from 2 to 4.     

沙蚕毒系仿生性农药(CH3)2NHCH(CH2S2O3)2NaH2O的电化学研究

杀虫单（ＣＨ３）２ＮＨＣＨ（ＣＨ２Ｓ２Ｏ３）２Ｎａ·Ｈ２Ｏ是我国独自开发的一种沙蚕毒系仿生性农药．我们用循环伏安法和计时库仑法研究了杀虫单的电极反应过程及在电位扫描速率,支持电解质ＰＨ以及浓度变化时对峰电流及峰电位的影响．研究表明杀虫单发生不可逆还原电极反应,还原产物二氢沙蚕毒素在电极上发生强吸附,其吸附量为８．２３×１０－１０ｍｏｌ／ｃｍ２．在随后的循环电位扫描中二氢沙蚕毒素氧化生成沙蚕毒素在循环伏安图上出现新电流峰．沙蚕毒素与二氢沙蚕素的峰电位相差３３ｍＶ,两者间有２电子可逆电极反应特征     

CH3 CH2 +N(4S)反应机理的理论研究

The reaction for CH3CH2+N(4S) was studied by ab initio method. The geometries of the reactants, intermediates, transition states and products were optimized at MP2/6-311+G(d,p) level. The corresponding vibration frequencies were calculated at the same level. The single point calculations for all the stationary points were carried out at the QCISD(T)/ 6-311+G(d,p) level using the MP2/6-311+G(d,p) optimized geometries. The results of the theoretical study indicate that the major products are the CH2CH2+3NH and H2CN＋CH3, and the minor products are the CH3CHN+H in the reaction. The majority of the products CH2CH2+3NH are formed via a direct hydrogen abstraction channel. The products H2CN＋CH3 are produced via an addition/dissociation channel. The products CH3CHN+H are produced via an addition/dissociation channel.     

CH3CH2+O(3P)反应机理的理论研究

The reaction for CH3CH2+O(3P) was studied by ab initio method. The geometries of the reactants, intermediates, transition states and products were optimized at MP2/6-311+G(d,p) level. The corresponding vibration frequencies were calculated at the same level. The single-point calculations for all the stationary points were carried out at the QCISD(T)/6-311+G(d,p) level using the MP2/6-311+G(d,p) optimized geometries. The results of the theoretical study indicate that the major products are the CH2O＋CH3, CH3CHO+H and CH2CH2+OH in the reaction. For the products CH2O＋CH3 and CH3CHO+H, the major production channels are A1: (R)→IM1→TS3→(A) and B1: (R)→IM1→TS4→(B), respectively. The majority of the products CH2CH2+OH are formed via the direct abstraction channels C1 and C2: (R)→TS1(TS2)→(C). In addition, the results suggest that the barrier heights to form the CO reaction channels are very high, so the CO is not a major product in the reaction.     

Reaction of chlorine with platinum(IV) triamine containing N,N-dimethylethylenediamine. The crystal structure of [Pt{(CH3)2N(CH2)2NH2}PyCl3]Cl·H2O[Pt{(CH3)2N(CH2)2NCl}PyCl3], and [Pt{(CH3)2N(CH2)2NH2}PyCl4]

The Platinum(II) diamine with N,N-dimethylethylenediamine (N,N-dimeEn) [Pt{(CH₃)₂N(CH₂)₂NH₂}Cl₂] (I) was synthesized. The reaction of the diamine with pyridine gave Pt(II) tetramine [Pt{(CH₃)₂N(CH₂)₂NH₂}Py₂]Cl₂ (II), which was oxidized with chlorine to give Pt(IV) triamine Pt{[(CH₃)₂N(CH₂)₂}PyCl₃]Cl · H₂O (III). The reaction of III with chlorine (chloroamidation) yielded chloroimide [Pt{(CH₃)₂N(CH₂)₂NCl}PyCl₃] (IV). The IR spectra of complexes I–IV and UV/Vis spectra of III and IV were studied. X-Ray diffraction analysis was performed for III (monoclinic crystals, space group P2₁/c, a = 7.7437(6), b = 8.1100(7), c = 28.52992(2) Å, β = 93.7280(10)°, Z = 4, R _hkl = 0.0420) and IV (orthorhombic crystals, space group Pna2₁, a = 15.7825(12), b = 7.4447(6), c = 12.3099(6) Å, Z = 4, R _hkl = 0.0539). During oxidation of Pt(II) tetramine with chlorine, the pyridine molecule is removed from the cis position relative to the (CH₃)₂N group (trans position relative to the NH₂ group) of N,N-dimethylethylenediamine. The reaction of chloroimide complex IV with concentrated HCl (dechloroamidation) at 20°C afforded the initial complex III; that at 100°C, gave triamine III together with Pt(IV) diamine [Pt(N,N-dimeEn)Cl₄] (V) (monoclinic crystals, space group P2₁/n, a = 7.1278(5), b = 11.5384(8), c = 12.7501(9) Å, β = 93.23(10)°, Z = 4, R _hkl = 0.0239).     

Co(III) and Cr(III) complexes of diphosphadithia ligands and the crystal structure of [CoCl2(L3)]PF6·CH2Cl2 (L3=Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2)

[CrX₃(thf)₃] (X=Cl or Br) reacts with L (L=L¹–L³ or Ph₂[14]aneP₂S₂) (L¹=Ph₂P(CH₂)₂S(CH₂)₂S(CH₂)₂PPh₂, L²=Ph₂P(CH₂)₂S(CH₂)₃S(CH₂)₂PPh₂, L³=Ph₂P(CH₂)₂S(o-C₆H₄)S(CH₂)₂PPh₂, Ph₂[14]aneP₂S₂=4,8-diphenyl-1,11-dithia-4,8-diphosphacyclotetradecane) and TlPF₆ in MeNO₂ solution to yield the distorted octahedral complexes [CrX₂(L)]PF₆ as green coloured solids in high yield. UV/visible spectroscopy suggests that these are cis-dihalo species and they have also been characterised by IR spectroscopy, electrospray mass spectrometry and microanalyses. The Co(III) analogues [CoX₂(L)]⁺ are readily prepared in a two-stage reaction, involving treatment of CoX₂·6H₂O with L (L=L¹–L³) and NH₄PF₆ in EtOH solution to give a green/brown solid, followed by halogen oxidation of this product in CH₂Cl₂ solution using X₂/CCl₄, to give the final products as brown coloured solids. A mixture of PF₆⁻ and [CoX₄]²⁻ anions are present in the final Co(III) compounds in varying ratios. Crystal structures of [CoCl₂(L²)]₂[CoCl₄]·4H₂O and [CoCl₂(L³)]PF₆·CH₂Cl₂ confirm tetradentate P₂S₂ coordination of L in each case, with mutually cis halogens completing the distorted octahedral geometry. In both cases the complex cation adopts the cis-α form in the solid state and this is also consistent with the solution ³¹P{¹H} NMR spectroscopic data. ⁵⁹Co NMR spectroscopy reveals a very broad single resonance at ≈3200 ppm for these species.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability Properties of the Complex [Cd2(phen)2(C14HuO3)4(CH3CH2OH)]·(CH3OH)·(H2O)

T A dinuclear cadmium complex[Cd2(phen)2(C14H11O3)4(CH3CH2OH)]·(CH3OH)·(H2O)has been synthesized with benzilic acid and 1,10-phenanthroline by hydrothermal method.The crystal structure was determined bv X-ray diffraction with crystal parameters as follows:triclinic system with space group P-1,α=1.21298(10),b=1.32586(1 1),c=2.4815(2)nm,α=76.2630(10),β=81.4500(10),γ=69.1700(10)°V=3.6143(5)nm3,Dc=1.438g/cm3,Z=1,F(000)=1600,the final GOOF=0.937,R=0.0521 and wR=0.1328.In the title complex,the dinuclear structure is defined by carboxyl oxygen atoms adopting a monodentate bridged coordination mode.The coordination environment of Cd(Ⅱ)ion is CdO4N2,giving a distorted octahedral coordination geometry.TG analysis shows that the title complex is stable under 140℃.     

反常蓝移单电子锂键Y…Li-CH3[Y=CH3, CH2CH3, CH(CH3)2, C(CH3)3]体系的结构与性质

在密度泛函理论B3LYP/6-311++G(d,p)及MP2/6-311++G(d,p)水平上研究了单电子锂键复合物Y…Li—CH3[Y=CH3, CH2CH3, CH(CH3)2, C(CH3)3]的结构与性质. 结果表明, 三种单电子锂键复合物H3CH2C…Li—CH3(II), (H3C)2HC…Li—CH3(III)和(H3C)3C…Li—CH3(IV)单电子锂键强度依II(-26.7 kJ·mol-1)相似文献