HO^3^5Cl,HO^3^7Cl,DO^3^5Cl和DO^3^7Cl的振动激发态光谱研究

本文用自洽场组态相互作用方法(SCF-CI)精确计算了次氯酸分子HOCl的振动激发态的能级以及次氯酸分子中的H和Cl分别被D和^3^7Cl取代后的HO^3^7Cl,DO^3^5Cl和DO^3^7Cl的同位素效应, 这些理论计算值与已有的实验结果吻合较好, 还预测了一些尚未观测到的谱线频率及同位素效应。     

Phase equilibria in the quaternary systems Li‖F,Cl,Br,CrO4 and Li‖F,Cl,Br,WO4

Phase equilibria in the quaternary systems Li‖F,Cl,Br,CrO₄ and Li‖F,Cl,Br,WO₄ were studied by differential thermal analysis. In these systems, the stability of continuous series of solid solutions based on lithium chloride and bromide is preserved. The number and compositions of crystallizing phases in the systems Li‖F,Cl,Br,CrO₄ and Li‖F,Cl,Br,WO₄ were confirmed by X-ray powder diffraction analysis.     

制Cl2,为什么要用浓盐酸

和强酸制弱酸,HCl NaCH3COO=NaCl CH3COOH,难溶物转化为更难溶物,AgCl NaI=NaCl AgI相同,氧化还原反应,如Cl2 2NaBr=2NaCl Br2,被氧化产物(Br2)的氧化性弱于使用的氧化剂(Cl2),被还原产物(NaCl)的还原性弱于原先的还原剂(NaBr)。显然,酸(碱)性强度、难溶的难溶程度、氧化性(还原性)倾向相差越大,以上诸反应越完全。     

Rules on intrapair and interpair correlation energy for Cl, Cl−and MCl (M=H, Li, Na, K)

According to the calculation results of the intrapair and interpair correlation energy for the title systems, it has been found that the intrapair correlation energy of K shell of Cl is almost a constant and both the intrashell and intershell correlation energy of K and L shell changes little. It has also been found that in MCl series compounds the value of Cl correlation energy contribution depends on the ionicity of MCl compounds, i.e., the Cl correlation energy contribution increases with the increase of the ionic bond strength of the compound and this value is always less than the correlation energy of Cl^- anion but always larger than that of Cl atom. These rules are helpful for the estimation of the correlation energy of ionic compounds and the energy changes of chemical reactions.     

F Cl_2→ClF Cl和Cl′F Cl→Cl′ ClF的反应机理

用密度泛函理论(DFT)B3LYP方法,取6-311G基组,计算研究了F＋Cl2→ClF＋Cl的反应机理.求得1个线形和2个三角形过渡态,反应能垒分别为1.24、46.37和105.09kJ·mol－1;同时发现F以∠FClCl为10～20°（或120～160°）进攻Cl2时,反应无能垒.此外,求得对称反应Cl′F＋Cl→Cl′＋ClF的能垒为40.57kJ·mol－1的1个过渡态.     

Chlorination of charged buckyballs: reactions of C60x+ cations (x = 1–3) with Cl2, CCl4, CDCl3, CH2Cl2, and CH3Cl

The chlorination of singly and multiply charged C₆₀ cations has been investigated with the selected-ion flow tube technique. Observations are reported for the reactions of C₆₀^·+, C₆₀²⁺ and C₆₀^·3+ with Cl₂, CCl₄, CDCl₃, CH₂Cl₂ and CH₃Cl at room temperature (295 ± 2 K) in helium at a total pressure of 0.35 ± 0.02 Torr. C₆₀^·+ and C₆₀²⁺ were observed not to chlorinate, or react in any other way, with these five molecules. Chlorine also did not react with C₆₀^·3+, but bimolecular chloride transfer and electron transfer reactions, reactions that result in charge reduction/charge separation, were observed to occur with CCl₄, CDCl₃, CH₂Cl₂ and CH₃Cl. Chloride transfer was the predominant channel seen with CCl₄, CDCl₃ and CH₂Cl₂ while electron transfer dominates the reaction with CH₃Cl. These results are consistent with trends in chloride affinity and ionization energy. The reluctant chlorination of the first two charge states of C₆₀ is attributed to the energy required to distort the carbon cage upon bond formation, while the observed chloride transfer to C₆₀^·3+ is attributed to the greater electrostatic interactions with this ion.     

35Cl, 93Nb, 181Ta,and 121Sb NQR in Cl5MV · OPCl3 (MV = Nb,Ta, Sb,or P) Complexes

The behavior of ³⁵Cl NQR spectra in Cl₅M · OPCl₃ complexes is affected by the nature of the metal center and the distortion of its surrounding geometry. In all cases considered, the ³⁵Cl NQR frequencies in the OPCl₃ fragment shift toward higher frequencies upon complex formation, whereas the frequencies of axial chlorine atoms in the Cl₅M group in the phosphorus and antimony complexes lie below those for the equatorial atoms, and in the niobium and tantalum complexes, the frequencies of the axial atoms are higher than those of the equatorial ones.     

Chemical interaction in the quaternary mutual systems Li,K‖F,Cl,MoO4 and Li,K‖F(Cl),VO3,MoO4

The Li,K‖Cl,VO₃,MoO₄ system was partitioned into simplexes using graph theory, and the tree of phases for this system was constructed. The equations of the main reactions describing the chemical interaction in the quaternary mutual systems Li,K‖F,Cl,VO₃(MoO₄) and Li,K‖F(Cl),VO₃,MoO₄ were derived using the conversion patterns of partitioning elements. Based on the reaction equations and the data on the boundary elements, the prediction of phases crystallizing in the studied systems was made and confirmed by X-ray powder diffraction analysis.     

Ag@AgX（Cl, Br, I）及其复合物光催化剂的研究进展

综述了Ag@AgX（Cl, Br, I）等离子体光催化剂及其以TiO2、BiOX、BiVO4、ZnO等为本体制备的一系列复合物的研究进展,光催化机理、光催化剂的应用等方面的内容,并展望了Ag@AgX（Cl、Br、I）及其复合物未来的发展方向和研究内容。     

The structures of X2[(Mo6Cl8)Cl6]·nH2O,X=NH4, K,Rb, Cs

The title compounds were synthesized from MoCl₂ and the appropriate commercial chlorides and their structures were solved by a combination of single crystal X-ray diffraction analysis and theoretical methods. The NH₄, K and Rb compounds are essentially isostructural, and crystallize in space group Ia (No. 9) with the cell parameters (in Å) a=9.173(1), b=14.986(2), c=17.505(3), β=92.94(2)° (NH₄); a=9.140(4), b=14.852(5), c=17.445(11), β=93.48(6)° (K); a=9.215(1), b=14.941(3), c=17.532(2), β=92.70(1)° (Rb); while the Cs compound crystallizes in space group P2₁/n (No. 14) with the cell dimensions a=9.771(3), b=12.984(4), c=21.535(4), β=90.81(3)°.     

Chemical effects of (n, γ) nuclear reaction on (Mo6Cl8)Cl4

The chemical effects of⁹⁸Mo(n, )⁹⁹ Mo reaction on molybdenum(II) chloride [(Mo₆Cl₈)Cl₄] have been studied. Retention, thermal and radiolytical annealing were determined. It was found that this molybdenum compound has low retention, a negligible tendency to thermal annealing and a virtual insensitivity to hydrolysis. For practical application in the enrichment of⁹⁹Mo by the Shilard-Chalmers method, molybdenum(II) chloride [(Mo₆Cl₈)Cl₄] appears to offer good prospects.     

Li,K‖Cl,MoO4 ternary mutual system

Phase equilibria in the Li,K‖Cl,MoO₄ ternary mutual system were studied by differential thermal analysis (DTA). The characteristics of the following three ternary eutectics were determined: E ₁: 348°C, 41 mol % KCl, 7.75 mol % Li₂MoO₄, and 51.25 mol % LiCl; E ₂: 475°C, 44 mol % KCl, 17.25 mol % Li₂MoO₄, and 38.75 mol % LiCl; and E ₂: 477°C, 35 mol % KCl, 47 mol % Li₂MoO₄, and 18 mol % LiCl.     

过渡金属M (M=Cu,Ag, Au)对X…Cl (X = F,Cl, Br)卤键相互作用强度的影响

采用量子化学方法,通过MCH2X…ClF(M=Cu,Ag,Au;X=F,Cl,Br)和CH3X…ClF两类复合物的对比,探讨了过渡金属对卤键相互作用强度的影响.CH3X…ClF复合物只有卤键相互作用,而优化MCH2X…ClF复合物除了得到一种只含有卤键相互作用的构型外,还得到一种含有过渡金属和Cl原子相互作用的稳定构型.含有过渡金属的复合物稳定性明显增加,Ag取代的复合物稳定性增加最为明显,Cu次之,Au最不明显.X原子最负分子表面静电势(MEP)减小是复合物稳定性增加的根本原因.利用自然键轨道(NBO)及分子中原子(AIM)分析进一步对体系的分子间相互作用进行了探讨.二阶稳定化能与键鞍点处拓扑性质的计算结果与相互作用能符合得很好.     

C28X4（X=H,Cl）,CX4（X=H,Cl）的结构和电子光谱的理论研究

用ＩＮＤＯ法对Ｃ２８Ｘ４（Ｘ＝Ｈ，Ｃｌ）和ＣＸ４（Ｘ＝Ｈ，Ｃｌ）进行几何构型优化，得到Ｔｄ对称性的构型Ｃ２８Ｘ４有４种键、４种不等同原子，基态为稳定的闭壳层分子，以此构型为基础计算了上述分子的电子光谱，并预测Ｃ２８Ｘ４的电子光谱。     

Organophosphines in PtPCOX (X = N,Cl, S), PtPCNX (X = Cl,S, Br,I, As) and PtPCClX (X = S,I, As) derivatives: structural aspects

In this review are classified and analyzed structural parameters of almost 90 monomeric organoplatinum complexes with inner coordination spheres consisting of PtPCOX (X?=?N, Cl, S), PtPCNX (X?=?Cl, S, Br, I, As) and PtPCClX (X?=?S, I, As). These complexes crystallized in three crystal systems: orthorhombic (× 11), triclinic (× 32) and monoclinic (× 45). Distorted square planar arrangements about the Pt(II) atoms are provided by mono-, heterobi- and heterotridentate donor ligands. The chelating ligands create a wide variety of four-, five- and six-membered metallocyclic rings and the effects of both steric and electronic factors influence the L–Pt–L bite angles. There are wide variations in the trans-positions of the donor ligands. Two examples are classified as distortion isomers.     

Bond distances and bond angles of the C10 skeleton in naphthalene derivatives as hard bond parameters:35Cl NQR and structure of 1,8-diaminonaphthalene · Cl2HCCOOH, 1,8-diaminonaphthalene · Cl3CCOOH, 1-aminonaphthalene · Cl3CCOOH,and 1,8-diaminonaphthalene

The structures of several naphthalene derivatives and their³⁵Cl NQR spectra have been investigated. 1,8-Diaminonaphthalene,C _2v ⁹ -Pna2 ₁, Z = 8,a (in pm) = 881,b = 1577,c = 1213; 1,8-diaminonaphthalene monodichloroacetate,C _2h ⁶ -C2/c, Z = 8,a = 2050,b = 584,c = 2333, (in degrees) = 110.1; 1,8-diaminonaphthalene monotrichloroacetate,C ₁ ¹ -P¯1, Z=2,a=1211,b=1062,c=589,=74.8,=80.1,=70.9; 1-aminonaphthalene trichloroacetate,D _2h ¹⁵ -Pbca, Z=8,a=2347,b=1289,c=889. The³⁵Cl NQR spectrum of 1,8-diaminonaphthalene monodichloroacetate is a doublet, the frequencies decreasing with increasing temperature from 77 to 217 K at which temperatureT _b the NQR signals bleach out. A³⁵Cl NQR triplet is found for 1,8-diaminonaphthalene monotrichloracetate in the range 77 77K 207 (=T _b ). 1-Amino-naphthalene trichloroacetate shows a³⁵Cl NQR triplet, too, withT _b = 136 K. Characteristic for the intermolecular interactions are hydrogen bonds in the chloroacetic acid salts; each NH₃ group forms three hydrogen bonds, and of the two oxygens one is involved in two such bonds, one in one bond. Thereby units of two cations and two anions are formed, and these dirners are connected to strings by hydrogen bonds. Additional van der Waals interactions between the chlorine atoms and the naphthalene ring system are observed. Comparison of the intramolecular bond distances C(i)-C(j) of the C₁₀ naphthalene skeleton for 41 naphthalene derivatives (present data and literature) shows that the bond distances C(i)-C(j)are little influenced by substitution, as is the mean bond length. Shorter and longer distances prove a partial localization of charge at C(1)-C(2), C(3)-C(4), C(5)-C(6), and C(7)-C(8). Regularities within the bond angles and characteristic influences of 1,8-disubstitution on it are discussed.     

Unexpected complexation of allylpseudothiohydantoin hydrochlorides towards CuX (X = Cl,NO3, ClO4, BF4, 1/2SiF6). The first known examples of joint CuI(Cl,ClO4) and CuI(Cl,BF4) π-complexes

By means of alternating current-electrochemical synthesis starting from a mixture of 2-imino-3-(prop-2-en-1-yl)-1,3-thiazolidin-4-one (3-allylpseudothiohydantoin, napt) and 2-allylamino-1,3-thiazol-4(5H)-one (allylaminopseudothiohydantoin, aapt) hydrochlorides and corresponding copper(II) salts five new π-complexes, [Cu(napt)Cl] (1), [Cu₂(aapt)₂Cl]NO₃ (2), [Cu₂(aapt)₂Cl]BF₄ (3), [Cu₂(aapt)₂Cl]ClO₄ (4) and [Cu₂(aapt)₂Cl]₂SiF₆·2H₂O (5), were obtained and studied by X-ray single crystal diffraction and IR-spectroscopy. Napt and aapt molecules are selectively coordinated to Cu⁺ depending on the anion type. In crystals of 1 and 5, the organic ligands are attached to the metal in a chelating N,(C=C)-bidentate mode. The aapt molecule in 2-4 acts as a tridentate chelating ligand, being coordinated to the copper(I) ion through the heterocyclic N atom, carbonyl O atom, and C=C bond of allyl group, forming an original cationic [Cu₂(aapt)₂Cl]⁺ fragment with both a bridging Cl^– ion and O atom of the C=O group. In the presence of the doubly charged SiF₆^2– anion, Cu(I) in 5 prefers to be bonded with two bridging Cl^– ions, rather than the C=O group, causing [Cu₂(aapt)₂Cl]⁺ units to associate into the infinite cationic chains. Crystals of 3 and 4 are the first known examples of the simultaneous BF₄^–/Cl^– or ClO₄^–/Cl^– participation in copper(I) π-complex formation.     

F＋Cl2->ClF＋Cl和Cl′F＋Cl->Cl′＋ClF的反应机理

用密度泛函理论(DFT)B3LYP方法,取6 311G基组,计算研究了F＋Cl2ClF＋Cl的反应机理.求得1个线形和2个三角形过渡态,反应能垒分别为1.24、46.37和105.09kJ•mol－1;同时发现F以∠FClCl为10～20°（或 120～160°）进攻Cl2时,反应无能垒.此外,求得对称反应Cl′F＋ClCl′＋ClF的能垒为40.57 kJ•mol－1的1个过渡态.     

Computational studies of σ-type weak interactions between NCO/NCS radicals and XY(X = H,Cl;Y = F,Cl,and Br)

The triatomic radicals NCO and NCS are of interest in atmospheric chemistry,and both the ends of these radicals can potentially serve as electron donors during the formation of σ-type hydrogen/halogen bonds with electron acceptors XY(X = H,Cl;Y = F,Cl,and Br).The geometries of the weakly bonded systems NCO/NCS···XY were determined at the MP2/aug-cc-pVDZ level of calculation.The results obtained indicate that the geometries in which the hydrogen/halogen atom is bonded at the N atom are more stable than those where it is bonded at the O/S atom,and that it is the molecular electrostatic potential(MEP)-not the electronegativity-that determines the stability of the hydrogen/halogen bond.For the same electron donor(N or O/S) in the triatomic radical and the same X atom in XY,the bond strength decreases in the order Y = F > Cl > Br.In the hydrogen/halogen bond formation process for all of the complexes studied in this work,transfer of spin electron density from the electron donor to the electron acceptor is negligible,but spin density rearranges within the triatomic radicals,being transferred to the terminal atom not interacting with XY.