Photolysis of alkyl iodides at 147.0 nm. The reaction H + CnH2n + 1I → HI + CnH2n + 1

The 147 nm (8.4 eV) photolysis of gaseous C₂H₅I, n-C₃H₇I, and sec-C₃H₇I was investigated in the presence of and absence of HI. The main overall processes are: These dissociative processes occur mainly as a result of initial cleavage of the weak C? I bond, followed by decomposition of the internally excited alkyl radicals. In all cases, approximately 5-10% of the alkyl radicals thus formed do not undergo dissociation at pressures around 3-7 torr. There is also evidence for the elimination of HI as well as C? C cleavage in the primary dissociation. The former is indicated by deuterium labeling experiments and the formation of cyclopropane (Φ = 0.04) as a product in the photolysis of n-C₃H₇I. Because the processes listed above provide a constant source of H atoms whose quantum yield can be exactly determined, it was feasible to obtain accurate values for k_a/k_b: For thermally equilibrated H atoms (300 K), k_a/k_b is 0.44 ± 0.04, 0.57 ± 0.06, 0.95 ± 0.1, and 0.024 ± 0.01 for C₂H₅I, n-C₃H₇I, sec-C₃H₇I, and C₂H₅Br, respectively.     

饱和烷烃分子C_nH_(2n+2)(n=4-6)的电子动量光谱(英文)

使用B3LYP/TZVP//B3LYP/aug-cc-pVTZ方法系统研究了饱和烷烃分子CnH2n+2(n=4-6)的轨道电子动量光谱,比较了同分异构体CnH2n+2(n=4-6)对轨道动量分布的影响.结合二维空间分析方法对电子在坐标空间中的密度分布进行了系统的研究.计算结果表明,最内价壳层电荷分布主要由s电子贡献,第二近邻芯价壳层则主要由p电子贡献,而其余的价壳层则为sp杂化.最内价轨道表现出最大的谱线强度并且远大于其它轨道的谱线强度,而且正烷烃的谱线强度要大于异烷烃等同分异构体的谱线强度,表现出了明显的与甲基移动的个数有关的性质.     

Alkyl telluraalkanoates CnH2n+1Te(CH2)mCOOR (R = CH3, C2H5 OR H)

Methyl telluraalkanoates, C_nH_2n+1Te(CH₂)_mCOOR (n, m: 4, 7; 6, 4; 6, 7; 6, 9; 7, 4; 8, 7; 11, 2; 11, 5; 18, 11) were synthesized in yields ranging from 33 to 82 percent based on the quantities of the methyl ω-bromoalkanoates substrates. Disodium ditelluride was obtained from tellurium and sodium in ethylenediamine and was treated with alkyl bromides to give dialkyl ditellurides. The crude ditellurides were reduced with NaBH₄ to the alkane tellurolates which were coupled with methyl ω-bromoalkanoates to give the methyl telluraalkanoates. Ethyl 4-tellurapentadecanoate was prepared similarly from ethyl 3-bromopropanoate. The telluraalkanoates were characterized by elemental analyses, mass spectrometry, NMR spectrometry, and UV and IR spectrophotometry. Telluraalkanoates radiolabeled with ^123mTe or other radioisotopes have been reported elsewhere to be preferentially taken up by the heart and promise to be useful as myocardial imaging agents.     

Reactions of O+ with CnH2n+2, n=2-4: a guided-ion beam study

We have measured absolute reaction cross sections for the interaction of O(+) with ethane, propane, and n-butane at collision energies in the range from near thermal to approximately 20 eV, using the guided-ion beam (GIB) technique. We have also measured product recoil velocity distributions using the GIB time-of-flight (TOF) technique for several product ions at a series of collision energies. The total cross sections for each alkane are in excess of 100 A(2) at energies below approximately 2 eV, and in each case several ionic products arise. The large cross sections suggest reactions that are dominated by large impact parameter collisions, as is consistent with a scenario in which the many products derive from a near-resonant, dissociative charge-transfer process that leads to several fragmentation pathways. The recoil velocities, which indicate product ions with largely thermal velocity distributions, support this picture. Several product ions, most notably the C(2)H(3) (+) fragment for each of the alkanes, exhibit enhanced reaction efficiency as collision energy increases, which can be largely attributed to endothermic channels within the dissociative charge-transfer mechanism.     

[Mn(H2O)4(C4N2H4)][C6H4(COO)2] – Ein eindimensionales Koordinationspolymer mit kettenartigen [Mn(H2O)4(C4N2H4)]n2n+ Polykationen

[Mn(H₂O)₄(C₄N₂H₄)][C₆H₄(COO)₂] – An One‐Dimensional Coordination Polymer with Chain‐like [Mn(H₂O)₄(C₄N₂H₄)]_n²ⁿ⁺ Polycations Orthorhombic single crystals of [Mn(H₂O)₄(C₄N₂H₄)][C₆H₄(COO)₂] have been prepared in aqueous solution at room temperature. Space group Imm2 (no. 44), a = 1039.00(6) pm, b = 954.46(13) pm, c = 737.86(5) pm, V = 0.73172(12) nm³, Z = 2. Mn²⁺ is coordinated in a octahedral manner by four water molecules and two nitrogen atoms stemming from the pyrazine molecules (Mn–O 215.02(11) pm; Mn–N 228.7(4), 230.7(4) pm). Mn²⁺ and pyrazine molecules form chain‐like polycations with [Mn(H₂O)₄(C₄N₂H₄)]_n²ⁿ⁺ composition. The positive charge of the polycationic chains is compensated for by phthalate anions, which are accomodated between the chains. The phthalate anions are linked by hydrogen bonds to the polycationic chains. Thermogravimetric analysis in air revealed that the loss of water of crystallisation and pyrazine occurs in two steps between 130 and 245 °C. The resulting sample was stable up to 360 °C. Further decomposition yielded Mn₂O₃.     

CTAB/CnH2n+1OH/H2O体系的热力学和电化学性质

微乳液通常由表面活性剂、助表面活性剂、油和水等四组分自发生成,注意到表面活性剂、助表面活性剂和水三组分体系与上述四组分体系在相行为及其物理化学性质上具有相似性,为方便起见,人们通常以此三组分体系为对象,研究四组分体系微乳液的有关性质,并亦将其称为微乳液[1].另一方面,助表面活性剂一般为具有中等碳链长度的直链饱和一元醇,但实验已经发现,即使是像乙醇这样的短链醇,也能以相当数量存在于胶束栅栏中形成膜相[2],或存在于两亲双层中形成层状液晶[3].本文以热力学方法与无探针循环伏安法研究了直链饱和一元醇对ＣＴＡＢ/醇(Ｃ2Ｈ…     

Electronic absorption spectra of the protonated polyacetylenes H2CnH+ (n = 4, 6, 8) in neon matrixes

Electronic absorption spectra of the protonated polyacetylenic chains H2CnH+ (n = 4, 6, 8) and the neutral H2C8H have been observed in 6 K neon matrixes after mass selection. The wavelength of the H2CnH+ electronic transitions depends quasi-linearly on n, typical of carbon chains. The origin band is at 286.0, 378.6, and 467.6 nm for n = 4, 6, and 8, respectively. Two ground-state vibrations of H2C4H+ in the IR absorption spectrum were also detected. On the basis of the spectroscopic trends and the assignment of the vibrational frequencies in the ground and excited electronic states, it is concluded that the H2CnH+ species are C(2v) linear carbon chains with one H atom on one end and two on the other.     

Collisional activation spectra. Behavior of [C3H7O]+ and other [CnH2n+1O]+ ions

Collisional activation spectra have identified (i) as Stable ion structures. Evidence is presented for a variety of pathway for their formation, including anchimeric assistance and hydrogen migration in less stable isomers. The fragmentation behavior of a number of [C_nH_2n+1O]⁺ isomers of n = 2 to 5 shows that extensive rearrangements are common, but that some reactions appear to be useful for ion structure elucidation. One reaction identified is unusual in that it represents the decomposition of an even-electron ion to yied an odd-electron ion product in significant abundance.     

A New Heteropolyoxotungstate with a Three-dimensional All-inorganic Framework [（C2H4N2）4（P4Co3W4O（28）H6）（H2C2O4）]n

A new heteropolyoxotungstate [(C2H4N2)4(P4Co3W4O28H6)(H2C2O4)]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006(17),b = 17.1006(7),c = 10.7525(5),V = 3144.2(2)3,Z = 4,Dc = 3.795 g·cm-3,F(000) = 3300,MoKα(λ = 0.71073 ),μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.     

GF Calculations for some tricyclic molecules: C3H6, C3H4, C2H4NH,C2H4O and C2H4S

We have functions expressed as antisymmetrized products of strongly orthogonal geminals have been evaluated for some three membered ring molecules. GF results are compared with previously computed SCF-MO results, obtained employing the same atomic basis. Transferability features of bonds and inner shells are shown.     

层状结构杂合物（CnH2n＋1 NH3）2 NiCl4（n ＝4，8，12）的合成与表征

采用低温固相合成法制备了3种有机／无机杂合物（ Cn H2n ＋1 NH3）2 NiCl4（ n ＝4,8,12）,通过元素分析、X 射线粉末衍射、红外光谱和紫外‐可见吸收光谱对杂合物进行了表征。实验结果表明,利用低温固相合成法可成功制备杂合物（Cn H2n ＋1 NH3）2 NiCl4（ n ＝4,8,12）,3种产物均具有明显的层状结构且分别属于单斜晶系、六方晶系和正交晶系。     

Hydrothermal Synthesis and Crystal Structure of a New Phosphonate： {[Cu（1,10-phen）]2-（H2O3PCH2C6H4C6H4CH2PO3H）2-（HO3PCH2C6H4C6H4CH2PO3H） }n

1 INTRODUCTION Metal organophosphonates have attracted considerable attention for over three decades due to their potential or practical applications, include- ing ion exchanges[1, 2], molecular sensors[3] and optics[4, 5]. Recently, a number of porous m…     

Infrared spectra of HC2-.(C2H2)n and O2-.(C2H2)n clusters (n=2-5)

We study the solvation of HC2- and O2- with acetylene ligands by means of midinfrared photodissociation spectroscopy in the CH stretching region, monitoring C2H2 evaporation upon infrared photon absorption by the parent cluster ions. Our findings are interpreted with the help of density functional theory. The infrared spectra indicate that while the binding generally occurs through ionic H bonds, there are two different classes of ligands which differ in their binding strength. This holds true for both core ions, even though their electronic structures and charge distributions are very different.     

Vibrational spectroscopy and structures of Ni+(C2H2)(n) (n =1-4) complexes

Nickel cation-acetylene complexes of the form Ni(+)(C(2)H(2))(n), Ni(+)(C(2)H(2))Ne, and Ni(+)(C(2)H(2))(n)Ar(m) (n = 1-4) are produced in a molecular beam by pulsed laser vaporization. These ions are size-selected and studied in a time-of-flight mass spectrometer by infrared laser photodissociation spectroscopy in the C-H stretch region. The fragmentation patterns indicate that the coordination number is 4 for this system. The n = 1-4 complexes with and without rare gas atoms are also investigated with density functional theory. The combined IR spectra and theory show that pi-complexes are formed for the n = 1-4 species, causing the C-H stretches in the acetylene ligands to shift to lower frequencies. Theory reveals that there are low-lying excited states nearly degenerate with the ground state for all the Ni(+)(C(2)H(2))(n) complexes. Although isomeric structures are identified for rare gas atom binding at different sites, the attachment of rare gas atoms results in only minor perturbations on the structures and spectra for all complexes. Experiment and theory agree that multiple acetylene binding takes place to form low-symmetry structures, presumably due to Jahn-Teller distortion and/or ligand steric effects. The fully coordinated Ni(+)(C(2)H(2))(4) complex has a near-tetrahedral structure.     

A theoretical study on the protonation of cycloalkanes CnH2n (n = 3 to 6)

Ab initio self-consistent-field molecular orbital calculations have been carried out for the C_nH_2n (n = 3 to 6) cycloalkanes and various conformers of their protonated forms. The calculated protonation energies for the sequence of conformers of the protonated forms follow the experimentally observed trend. Correlations between optimum C? C? C bond angles at the protonation site and the calculated protonation energies have been observed, and these correlations may be of some use in estimating protonation energy-bond angle relations in other (strained) cyclic compounds when the central carbon atom of a C? C? C moiety is protonated.