不同类型的CO32-替换羟基磷灰石固溶体晶体化学FT-IR研究

利用FT-IR结合XRD对不同类型的CO₃^2-替换磷灰石固溶体进行了晶体化学研究,结果表明:B型替换碳羟磷灰石(CHAP)的替换方式是[CO₃·OH]四面体替换[PO₄]四面体;A型替换CHAP的替换方式是[CO₃]三角形配位体替换通道位置的OH^-;AB混合型替换CHAP的FT-IR谱中非对称伸缩振动ν₃分裂为ν_3-1、ν_3F、ν_3-4,高斯函数法拟合表明ν_3F峰是A型替换的ν_3-2与B型替换的ν_3-3的叠合。当W_CO3^2-≦3.34%时,随CO₃^2-含量增加,A型替换量增大,替换指数(SI)增大,且当W_CO3^2-=3.34%时,SI达最大值,当3.34%CO₃^2-≦7.52%时,随CO₃^2-含量增加,SI减小,B型替换量增大,且当W_CO3^2-=7.52%时总固溶量饱和。     

[Co(ptma)(amp)Cl]2+体系的一反式经式异构体(m3[ZnCl4]·0.5H2O)的晶体结构

在合成[Co(bpma)(tn)Cl]²⁺体系配合物的实验中,得到[Co(ptma)(amp)Cl]²⁺体系的一反式(ptma中仲胺上的氢相对于Cl)经式异构体(m3[ZnCl₄]·0.5H₂O),其中bpma=N,N′-二(2-吡啶基甲基)胺,tn=1,3丙二胺,ptma=N-(2-吡啶基甲基)丙二胺,amp=2-(氨基甲基)吡啶。此配合物异构体构型选择性形成的原因可能主要是其结构中配体间C-H…π相互作用使之更稳定的结果。利用单晶X-射线衍射法测定的晶体学参数:单斜晶系,空间群C2/c,a=1.55978(19)nm,b=1.33324(16)nm,c=2.2077(3)nm,β=94.832(3)°,V=4.5748(10)nm³,D_c=1.696g·cm^-3,Z=8,F₀₀₀=2360,μ(MoKα)=23.72cm^-1,R=0.0475,R_w=0.1204。配合物离子中Co³⁺为六配位。晶胞中含8个配合物阳离子,8个[ZnCl₄]^2-阴离子及4个水分子,对映体的比例为1∶1。     

含大环[Ni([15]aneN5]2+氰基桥联四核簇合物的合成、结构和磁性质

用1,4,7,10,13-五氮十五烷(cpad)作为端基配体,合成了2个同构化合物[{Ni(cpad)}₃M(CN)₆]₂[M(CN)₆](ClO₄)₃·6H₂O (M=Cr³⁺,1;Fe³⁺,2),其中[M(CN)₆]^3-通过氰基桥联配位,4个[Ni(cpad)]²⁺阳离子形成四核簇[{Ni(cpad)}₃M(CN)₆]³⁺,游离的[M(CN)₆]^3-和ClO₄^-为平衡阴离子。晶体参数如下：1,三方晶系,P3c1空间群,a=1.5144 1(18) nm,c=3.080 7(6) nm,V=6.118 9(15) nm³,Z=2;2,三方晶系,P3c1空间群,a=1.4976 2(17) nm,c=3.087 8(5) nm,V=5.997 6(14) nm³,Z=2。变温磁化率显示在四核簇内氰基桥联的金属离子之间存在铁磁相互作用。     

以2,4,4’-联苯三羧酸及2,2’-联吡啶构筑的三维钴(Ⅱ)配位聚合物的合成、晶体结构及磁性质

通过水热方法,以2,4,4’-联苯三羧酸（H₃btc）和2,2’-联吡啶（2,2’-bpy）与CoCl₂·6H₂O反应,合成了1个具有三核钴单元的三维配位聚合物[Co_1.5（btc）（2,2’-bpy）_0.5（2H₂O）]_n,并对其结构和磁性质进行了研究。结构分析结果表明该聚合物的晶体属于单斜晶系,I2/a空间群,a=1.7744（4）nm,b=1.1423（2）nm,c=1.8908（4）nm,β=105.18（3）°,V=3.6985（13）nm³,D_c=1.745g·cm^-3,Z=8,R=0.0484,wR=0.0852（I>2σ（I））。来自4个不同btc^3-配体的4个羧基连接相邻的3个钴（Ⅱ）离子形成了1个三核钴（Ⅱ）的结构单元。这些三核钴（Ⅱ）的结构单元又通过btc^3-配体与钴（Ⅱ）离子的配位作用形成了1个三维的框架。研究表明,该聚合物中相邻钴（Ⅱ）离子之间存在铁磁相互作用。     

茂基稀土邻氨基苯甲酰胺基双负离子配合物的合成及其环胺羰化反应和脒基化反应

Cp₃Ln与邻氨基苯甲酰胺在甲苯中反应,之后在HMPA和甲苯中结晶,以中等到高收率得到四核稀土有机配合物[CpLn（μ-η²：η²-NHC₆H₄CONH）（μ₃-η¹：η¹：η²-NHC₆H₄CONH）LnCp（HMPA）}₂（Ln=Yb,1a;Er,1b;Y,1c）。化合物1与4倍物质的量的PhNCO在甲苯中反应形成1,3-喹唑啉二氧基（Quo）双负离子稀土配合物[Cp₂Ln（μ₃-η²：η²：η¹-Quo）]₃Ln（HMPA）₂（Ln=Yb,2a;Er,2b;Y,2c）,表明化合物1中的Ln-NHAr键和ArCONH-Ln键能与异氰酸酯分子发生连续加成/胺消除反应,形成1,3-喹唑啉二氧基骨架。但化合物1a~1c与ⁱPrN=C=NⁱPr反应,仅得到ArNH基单加成产物{Cp₂Ln[μ-η³：η¹-ⁱPrNC（NHⁱPr）NC₆H₄CONH]}₃Ln（HMPA）₃ （Ln=Yb,3a;Er,3b;Y,3c）。而Cp3Ln与邻氨基苯甲酰胺和ⁱPrN=C=NⁱPr在甲苯中进行"一锅"反应,则形成双核配合物{CpLn[μ-η³：η²-NHCOC₆H₄NC（NHⁱPr）NⁱPr]}₂（Ln=Yb,4a;Er,4b;Y,4c）。值得注意的是,HMPA能够诱导配合物4发生配体重排反应,转化成化合物3。     

茂基稀土邻氨基苯甲酰胺基双负离子配合物的合成及其环胺羰化反应和脒基化反应

Cp₃Ln与邻氨基苯甲酰胺在甲苯中反应,之后在HMPA和甲苯中结晶,以中等到高收率得到四核稀土有机配合物[CpLn（ μ-η²：η²-NHC₆H₄CONH）（ μ₃-η¹：η¹：η²-NHC₆H₄CONH）LnCp（HMPA）}₂（Ln=Yb,1a;Er,1b;Y,1c）。化合物 1与4倍物质的量的PhNCO在甲苯中反应形成1,3-喹唑啉二氧基（Quo）双负离子稀土配合物[Cp₂Ln（ μ₃-η²：η²：η¹-Quo）]₃Ln（HMPA）₂（Ln=Yb,2a;Er,2b;Y,2c）,表明化合物1中的Ln-NHAr键和ArCONH-Ln键能与异氰酸酯分子发生连续加成/胺消除反应,形成1,3-喹唑啉二氧基骨架。但化合物1a~1c与ⁱPrN=C=NⁱPr反应,仅得到ArNH基单加成产物{Cp₂Ln[ μ-η¹：η¹：η²-ⁱPrNC（NHⁱPr）NC₆H₄CONH]}₃Ln（HMPA）₃ （Ln=Yb,3a;Er,3b;Y,3c）。而Cp₃Ln与邻氨基苯甲酰胺和ⁱPrN=C=NⁱPr在甲苯中进行“一锅”反应,则形成双核配合物{CpLn[ μ-η¹：η²：η²-NHCOC₆H₄ NC（NHⁱPr）NⁱPr]}₂（Ln=Yb,4a;Er,4b;Y,4c）。值得注意的是,HMPA 能够诱导配合物4发生配体重排反应,转化成化合物3。     

由2-甲基咪唑-4, 5-二羧酸构筑的双核平行六面体三维钙配位聚合物

合成了一个双核钙配合物{[Ca₂(μ₃-HMIA^2-)(μ₅-HMIA^2-)(H₂O)]·H₂O}_n(1, H₃MIA=2-甲基咪唑-4, 5-二羧酸), 并用元素分析、红外光谱和X-射线单晶衍射等对其进行了表征。结构分析表明, 1属单斜晶系, P2₁/c空间群, 晶胞参数为a=0.860 67(11) nm, b=1.656 5(2) nm, c=1.269 24(16) nm, β=108.005 0(10)°, V=1.720 9(4) nm³, C₁₂H₁₀Ca₂N₄N₁₀, M_r=450.40, Z=4, D_c=1.728 g·cm^-3, F(000)=920, μ=0.727 mm^-1, S=1.041, λ(Mo Kα)=0.071 073 nm, R=0.026 0 and wR=0.063 8。在1晶体结构中, 每个钙(Ⅱ)离子都是7配位的, 但展现2个不同的配位环境。4个μ₃-HMIA^2-配体, 2个μ₅-HMIA^2-配体和8个钙(Ⅱ)离子一个平行六面体结构[Ca₈( μ₃-HMIA)₄ (μ₅-HMIA)₂]⁴⁺。μ₅-HMIA^2-配体采用独特的配位模式并连接周围的平行六面结构形成一维链结构, 配体μ₃-HMIA^2-连接相邻的一维链形成一种新的蜂窝型的二维层状结构, 相邻的二维层通过μ₃-HMIA^2-配体的2个氧原子进一步形一个三维结构。还研究了配合物1的热重分析和抑菌活性。     

碱性介质中二(高碘酸根)合铜(Ⅲ)酸根氧化乙二醇独丁醚的反应动力学及机理

在25℃～40℃区间用分光光度法在碱性介质中研究了二(高碘酸根)合铜(Ⅲ)酸根配离子(DPC)氧化乙二醇独丁醚(EGB)的反应动力学。结果表明:反应对DPC为一级,对EGB是1< n_ap< 2(n_ap代表表观反应级数);在保持准一级条件([EGB]₀ 》[Cu(Ⅲ)]₀)下,表观速率常数,k_obs,在弱碱性介质中,随[OH^-]增大而减小,在较强碱性介质中随[OH^-]增大而增大,随着[IO₄^-]增加而减小;无盐效应。提出了含有自由基过程的反应机理,由假设的两种同时进行的反应机理推出的速率方程能很好的解释全部实验现象,进一步求得速控步的速率常数和活化参数。     

两个基于二噻吩乙烯结构单元双核钌乙烯配合物的合成, 表征和性质

合成了2个含二噻吩乙烯结构单元双核钌乙烯配合物[RuCl（CO）（PMe₃）₃]₂（μ-2,2’-（CH=CH）^2-DTE）（1a）和[RuCl（CO）（PMe₃）₃]₂（μ-2,5-（CH=CH）₂-DTE）（1b）,利用元素分析、红外、核磁共振谱和电化学对它们的结构进行了表征,X-射线单晶衍射分析表明,配合物1a晶体属单斜晶系,C2/c空间群,晶胞参数为：a=3.44575（6）nm,b=1.45945（2）nm,c=2.32191（5）nm,β=110.9770（10）°,V=10.9028（3）nm³,Z=8,D_c=1.467g·cm^-3,λ=0.071073nm,μ（MoKα）=0.956mm^-1,F（000）=4912。测定了它们光照前后的紫外-可见吸收光谱变化图,并对其光致变色性质进行了讨论。     

基于3, 3’, 5, 5’-(1, 3-苯基)-联苯四羧酸构筑的两个配位聚合物的合成、晶体结构和荧光性质

以3,3’,5,5’-（1,3-苯基）-联苯四羧酸（H₄btb）与1,10-菲咯啉（phen）为配体,分别与硝酸镉和硝酸锌在水热条件下反应合成2个一维[Cd（H₂btb）（phen）]_n（1）和二维{[Zn₂（btb）（phen）]·1.5H₂O}_n（2）配位聚合物,并对其进行了元素分析、红外光谱、热重分析和X-射线单晶衍射测定。配合物1属于单斜晶系,空间群为C2/c,晶胞参数：a=2.82845（13）nm,b=1.08554（5）nm,c=1.81768（8）nm,β=96.4850（10）°,V=5.5453（4）nm³,Z=8,D_c=1.670Mg·m^-3,F（000）=2800,R₁=0.0339,wR₂=0.0718[I >2σ（I）],配体H₄btb的2个羧基分别采取μ₁-η¹：η¹、μ₂-η²：η¹配位模式连接镉原子形成一维带状结构。化合物2也属于单斜晶系,空间群为P2₁/c,晶胞参数：a=1.7471（3）nm,b=1.2511（2）nm,c=2.1870（3）nm,β=120.911（11）°,V=4.1014（11）nm³,Z=4,D_c=1.491Mg·m^-3,F（000）=1876,R₁=0.0673,wR₂=0.1749[I>2σ（I）],全部去质子的H₄btb配体的4个羧基分别采取μ₁-η¹：η⁰、μ₁-η¹：η¹、μ₂-η¹：η¹配位模式连接锌原子形成一维链,链间通过μ₂-η¹：η¹桥连羧基扩展为（3,5）-连接的二维（4²·6⁷·8）（4²·6）网状结构。同时研究了2个配合物的荧光性质。     

Free‐volume variation in polyethylenes of different crystallinities: Positron lifetime,density, and X‐ray studies

High‐quality positron lifetime measurements (70 million total counts) are reported for polyethylenes (PEs) of different crystallinities (X_c = 3–82%). The specific volumes of the crystalline and amorphous phases (V_c and V_a, respectively) were estimated from density and wide‐angle X‐ray scattering (WAXS) experiments. Some samples (those with low values of X_c) were branched PEs, and those with high values of X_c were linear PEs for which X_c was varied with changes in the crystallization temperature. Both V_c and V_a increase with decreasing X_c in the range 0% ≤ X_c ≤ 56% (the branched PEs) but are constant for X_c ≥ 56% (the linear PEs). The lifetime spectra were analyzed with the MELT and LIFSPECFIT routines. Artifacts that can appear in the spectrum analysis were checked via an analysis of computer‐generated spectra. Four lifetime components appeared in all of the PEs; the two long‐lived ones are attributed to pick‐off annihilation of ortho‐positronium (o‐Ps) in crystalline regions (τ₃) and in holes of the amorphous phase (τ₄). With increasing X_c, τ₃ decreases from about 1.2 to 1 ns, τ₄ decreases from 3.0 to 2.5 ns, and the intensity I₄ decreases from 29 to 0%. An increase in I₃ from 6 to 12% was observed. A comparison with simulations shows that the true I₃ value approaches 0 for X_c → 0%. The decrease in I₄ is weaker than the increase in X_c; this leads to the conclusion that the apparent specific o‐Ps yield in the amorphous phase I₄^Xc increases with X_c. Possible reasons for this surprising results are discussed. The fractional free hole volume [h = (V_a ? V_occ)/V_a, where V_occ is the crystalline occupied volume] was estimated from density and WAXS results. Between X_c = 0 and 56%, h decreases from 0.151 to 0.090, but it does not change further above X_c = 56%. The mean size (v) of the local free volumes (holes) estimated from τ₄ decreases from 200 to 150 ų. The number density of holes (N_h) calculated from these values (N_h = h/v) also decreases from 0.8 to 0.6 nm^?3 in the range 0% ≤ X_c ≤ 56%. The values of V_a, V_c, h, and N_h increase with an increasing degree of branching but do not vary for linear PEs. The possible influence of a crystalline–amorphous interfacial phase (three‐phase model) on the observed lifetime parameters is also discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 65–81, 2002     

杯[4]吡咯-卤素、铵离子复合物的理论研究

采用密度泛函理论的M06-2X/6-31G(d, p)方法对杯[4]吡咯(CP)与卤素离子(X^-=F^-, Cl^-, Br^-)及卤素-铵根离子对的各种可能组装体系进行了系统研究. 详细讨论了各体系的结构、结合能、自然键轨道分析(NBO)和Multiwfn波函数分析的情况. 结果显示杯[4]吡咯与卤素阴离子的相互作用主要是氢键, 波函数分析显示在CPCl-和CP-Br-复合物中长程范德华力和空间位阻作用也明显存在. 杯[4]吡咯能与卤素-铵根离子形成稳定的复合物, 主要通过氢键作用、阴-阳离子的静电作用以及阳离子-π相互作用.从理论上探讨了杯[4]吡咯与离子或离子对的2:1组装体系,但相对于1:1组装体系来讲, 2:1体系并不占优势.本文结果进一步表明, 杯[4]吡咯不仅是一种阴离子受体,而且也是一种良好的离子对受体,尤其是对涉及氟离子的客体,更是如此.     

Structure and Bonding of the Mixed‐Valent Platinum Trihalides,PtCl3 and PtBr3

The isotypical crystal structures of the mixed valent trihalides PtCl₃ and PtBr₃ were redetermined by single crystal methods (space group R3¯; trigonal setting; PtCl₃: a = 21.213Å, c = 8.600Å, c/a = 0.4054; Z = 36; 1719 hkl; R = 0.035; PtBr₃: a = 22.318Å, c = 9.034Å; c/a = 0.4048; Z = 36; 1606 hkl; R = 0.027). A cubic closest packing of X^— anions forms the basis of an optimized arrangement of cuboctahedrally [Pt₆X₁₂] cluster molecules with Pt^II and enantiomers of helical chains of edge‐condensed [PtX₂X_4/2] octahedra with Pt^IV in cis‐Δ‐ and cis‐Λ‐configuration, respectively. The bond lengths vary with the function of the X^— ligands (d¯(Pt^II—X) = 2.315 and 2.445Å; d¯(Pt^II—Pt^II) = 3.336 and 3.492Å; d(Pt^IV—X) = 2.286 — 2.417Å and 2.437 — 2.563Å). The Pt^II atoms are shifted outwards the X₁₂ cuboctahedra by 0.045Å and 0.024Å, respectively. The symmetry governed Periodic Nodal Surface, PNS, perfectly separates the regions of different valencies. Quantum chemical calculations exclude the possible additional interactions between Pt^II and one of the exo‐ligands of Pt^IV.     

Rhodium(I) carbonyl complexes of tetradentate chalcogen functionalized phosphines, [P(X)(CH2CH2P(X)Ph2)3] {X = O, S, Se}: Synthesis, reactivity and catalytic carbonylation reaction

The reaction of [Rh(CO)₂Cl]₂ with 0.5 mol equivalent of the ligands [P^′(X)(CH₂-CH₂P(X)Ph₂)₃](P^′P₃X₄) {where X = O(a), S(b) and Se(c)} affords tetranuclear complexes of the type [Rh₄(CO)₈Cl₄(P^′P₃X₄)] (1a-1c). The complexes 1a-1c have been characterized by elemental analyses, mass spectrometry, IR and multinuclear NMR spectroscopy, and the ligands b and c are structurally determined by single crystal X-ray diffraction. 1a-1c undergo oxidative addition (OA) reactions with CH₃I to generate Rh(III) oxidised products. Kinetic data for the reaction of 1a and 1b with excess CH₃I indicate a pseudo first order reaction. The catalytic activity of 1a-1c for the carbonylation of methanol to acetic acid and its ester show a higher Turn Over Frequency (TOF = 1349-1748 h⁻¹) compared to the well-known species [Rh(CO)₂I₂]⁻ (TOF = 1000 h⁻¹) under the similar experimental conditions. However, 1b and 1c exhibit lower TOF than 1a, which may be due to the desulfurization and deselinization of the ligands in the respective complexes under the reaction conditions.     

Structural Studies of New Sulfito Mercurates(II) with General Formula xM[XHgSO3]middot;yHgX2·zMX·nH2O (M = NH4, K; X = Cl,Br)

Several solid phases with the general formula xM[XHgSO₃]·yHgX₂·zMX·nH₂O were obtained from aqueous solutions during phase formation studies in the systems M₂SO₃/HgX₂ (M = NH₄, K; X = Cl, Br). All phases were structurally characterized on the basis of single crystal X‐ray diffraction data and adopt new structure types. Compounds with x, y, z = 1 and n = 0 are isostructural (structure type I ) and crystallise with two formula units in space group P2₁/m and lattice parameters of a ≈ 9.7, b ≈ 6.2, c ≈ 10.4Å, β ≈ 111°. Compounds with x, y = 1 and z, n = 0 (structure type II ) crystallize in space group Cmc2₁ with four formula units and lattice parameters of a ≈ 5.9, b ≈ 22.0, c ≈ 6.9Å. The structures with x = 2, y, z = 1 and n = 0 are likewise isostructural (stucture type III ) and consist of four formula units in space group Pnma with lattice parameters of a ≈ 22.2, b ≈ 6.1, c ≈ 12.4Å. K[HgSO₃Cl]·KCl·H₂O is the only representative where x = 1, y = 0, z = 1 and n = 1 (structure type IV ). It is triclinic (space group ) with four formula units and lattice parameters of a = 6.1571(8), b = 7.1342(9), c = 10.6491(14) Å, α = 76.889(2), β = 88.364(2), γ = 69.758(2)°. Characteristic for all structures types is the segregation of the M⁺ cations and the anions and/or HgX₂ molecules into layers. The [XHgSO₃]⁻ anions are present in all structures and have m symmetry, except for K[HgSO₃Cl]·KCl·H₂O with 1 symmetry (but very close to m symmetry). The different [XHgSO₃] units exhibit very similar Hg‐S distances (average 2.372Å) and are more or less bent with ∠(X‐Hg‐S) angles ranging from 159.7 to 173.7°. The molecular HgX₂ entities present in structure types I ‐ III deviate only slightly from linearity with ∠(X‐Hg‐X) angles ranging from 174 to 179°. The structures are stabilised by interaction of the K⁺ or NH₄⁺ cations that are located between the anionic layers or in the vacancies of the framework, by K‐O contacts or, in case of ammonium compounds, by medium to weak hydrogen bonding interactions of the type N‐H···O.     

Carbonyl complexes of manganese, rhenium and molybdenum with 2-pyridylimino acid ligands

[MBr(CO)₃{κ²(N,O)-pyca}] [M = Mn(1a), Re(1b), pyca = pyridine-2-carboxaldehyde] and [MoCl(η³-C₃H₄Me-2)(CO)₂{κ²(N,O)-pyca}] (1c) react with aminoacid β-alanine to give the corresponding iminopyridine complexes 2a-2c. The same method affords the iminopyridine derivatives from γ-aminobutyric acid (GABA) (3a-3c) and 3-aminobenzoic acid (4a-4c). For complexes 2a-2c, 3a, 3c and 4a, the solid state structures have been determined by X-ray crystallography, revealing interesting differences in their hydrogen-bonding patterns in solid state.     

High-pressure high-temperature synthesis and crystal structure of the isotypic rare earth (RE)-thioborate-sulfides RE9[BS3]2[BS4]3S3, (RE=Dy-Lu)

Application of high-pressure high-temperature conditions (3.5 GPa at 1673 K for 5 h) to mixtures of the elements (RE:B:S=1:3:6) yielded crystalline samples of the isotypic rare earth-thioborate-sulfides RE₉[BS₃]₂[BS₄]₃S₃, (RE=Dy-Lu), which crystallize in space group P6₃ (Z=2/3) and adopt the Ce₆Al_3.33S₁₄ structure type. The crystal structures were refined from X-ray powder diffraction data by applying the Rietveld method. Dy: a=9.4044(2) Å, c=5.8855(3) Å; Ho: a=9.3703(1) Å, c=5.8826(1) Å; Er: a=9.3279(12) Å, c=5.8793(8) Å; Tm: a=9.2869(3) Å, c=5.8781(3) Å; Yb: a=9.2514(5) Å, c=5.8805(6) Å; Lu: a=9.2162(3) Å, c=5.8911(3) Å. The crystal structure is characterized by the presence of two isolated complex ions [BS₃]^3- and [BS₄]^5- as well as [□(S^2-)₃] units.     

12-钨磷酸钙与丁二酰亚胺加合物的制备和性质研究

本文研究了12-钨磷酸钙与丁二酰亚胺和邻苯二甲酰亚胺的加合反应,制备了12-钨磷酸钙的丁二酰亚胺加合物Ca_(3/2)PW_(12)O_(40)·4(CH_2CO)_2NH·7H_2O,测定了加合物的红外光谱、拉曼光谱和热重差热分析曲线,用X射线粉末衍射方法研究了加合物的结晶学特征.结果表明.配体丁二酰亚胺以一个羰基氧与金属阳离子配位,加合物的形成对杂阴离子的Kcggin结构没有明显影响.但WO_6八面体发生一定的畸变.其中W-O_d键减弱,W-O_c键增强.加合物属单斜晶系,晶胞参数为:a=25.839(6).b=13.223(2),c=18.438(2)(?),β=97.06(2)°,V=6251.88(?)~3,可能的空间群为C_2h~5-P2_1/c或C_2h~2-P2_1/m或C_2~2-P2_1,品质因子F_(30)=54(0.012,45).     

[1,2,3]Triazoloazine/(Diazomethyl)azine Valence Tautomers from 5-Azinyltetrazoles

[1,2,3]Triazoloazines are formed by thermolysis of 5-azinyltetrazoles in the gasphase or in solution. Thus, 5-(2-pyridyl)tetrazole ( 7 ) and 5-(2-pyrazinyl)tetrazole ( 11 ) yield [1,2,3]triazolo[1,5-a]pyridine ( 9 ) and [1,2,3]triazolo[1,5-a]pyrazine ( 13 ), respectively, at 400°/10^?3 - 10^?5 Torr. 5-(2-Phenyl-4-quinazolinyl)tetrazole ( 15 ) gives 5-phenyl[1,2,3]triazolo[1,5-c]quinazoline ( 17 ) in 75% yield by heating under reflux in mesitylene solution. 2-(Diazomethyl)pyridine ( 8 ), a valence tautomer of 9 , can be trapped by fumaronitrile, leading to 3-(2-pyridyl)-1, 2-cyclopropanedicarbonitrile ( 19 ). The [1,2,3]triazoloazines undergo base catalysed H/D-exchange in D₂O solution.     

Synthesis and Crystal Structures of New Palladium(II)—Gallium(III) Complexes with Bridging Halogenide Ligands

The reaction of palladium(II) bromide or palladium(II) iodide with the respective gallium(III) halogenide in the presence of aromatic solvents leads to the formation of palladium(II) tetrabromo— and tetraiodogallate. The compounds are isostructural {monoclinic, C2/m, Pd[GaBr₄]₂: a = 1267(2), b = 808(1), c = 722(1) pm, β = 94.5(1)°; Pd[GaI₄]₂: a = 1363(1), b = 849.9(4), c = 756.6(7) pm, β = 95.38(3)°}. The structures contain mononuclear complexes Pd[GaX₄]₂, where X^— = Br^— ( 1 ), I^— ( 2 ). The crystal structures of 1 and 2 were determined by single‐crystal X‐ray diffraction. Crystals of both compounds turned out to be similarly twinned.