双胺配体[K2(L)(THF)2](L=Ph2Si(NAr)2, Ar=2, 6-iPr2C6H3) 构筑的两个低价稀土镱化合物

以双胺类配体[K₂(L)(THF)₂] (1)(L=Ph₂Si(NAr)₂, Ar=2, 6-ⁱPr₂C₆H₃)与二价稀土YbI₂(THF)₂的交换反应得到2个不同类型的化合物[Yb(L)(THF)₃] (2)和{Yb(L)₂[K(THF)₂]₂} (3)。对化合物进行X-射线单晶结构解析, 核磁共振和元素分析表征。研究结果表明：化合物2中, 通过1个双齿含氮配体和3个中性THF分子配位, 以五配位模式稳定二价镱稀土中心。而化合物3中二价稀土镱是与2个螯合胺类配体配位, 以共平面、四配位模式稳定其金属中心。K+恰好在配体的2个苯环之间, 形成独特的三明治结构, 有助于化合物的稳定。     

原位产生的SO42-配位的二维无机钴配合物K2[Co3(OH)2(SO4)3(H2O)2]的水热合成及晶体结构

相同的水热反应条件下4-氨基-二(2-吡啶基)-1，2，4-三氮唑(abpt)、KSCN与钴盐(CoCl₂·6H₂O)反应合成了2种新的钴配合物:零维的单核配合物[CoSCN(abpt)] (1α)和二维的无机层状配合物K₂[Co₃(OH)₂(SO₄)₃(H₂O)₂] (1β)，并通过元素分析和红外光谱对其进行了表征。配合物1α的晶体属于单斜晶系，P2₁/c空间群。配合物1β晶体属于正交晶系，Cmc2₁空间群。在配合物1α中，abpt和SCN^-配体都参与配位与Co(Ⅱ)离子形成了2个不同的单核单元，这些单核单元又通过S原子和N原子之间的氢键作用连成了三维超分子结构;在配合物1β中，abpt配体没有参与配位，而SCN^-配体则被氧化成了SO₄^2-离子并与Co(Ⅱ)离子配位形成了二维配位层状结构，相邻层之间进一步通过氢键作用形成了沿c轴方向有孔道的三维超分子网络，这些孔道里面填充着反离子K+。     

二维网状配合物[Co(dimb)2(MeOH)2](ClO4)2的合成及晶体结构

设计并合成了一个含咪唑基团的柔性双齿配体:1,3-二(咪唑基-1′-甲基)-5-甲基苯(dimb)(1),并进行了 ¹H NMR和结构表征。通过dimb与高氯酸钴的反应,得到了一个新型的具有二维网状结构的配合物:[Co(dimb)₂(MeOH)₂](ClO₄)₂(2)。X-射线晶体结构测定表明,这两个化合物的晶体学参数分别为:配体(1)属单斜晶系, 空间群     

N，N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸的双核镍化合物Ni2(bbimp)2(4，4′-bipy)(H2O)2·2H2O和Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O

该文报道了N，N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸{bbimpH₂，[(C₇H₅N₂)CH₂]₂NCH₂PO₃H₂}的2个镍化合物Ni₂(bbimp)₂(4，4′-bipy)(H₂O)₂·2H₂O (1)和[Ni₂(bbimp)₂(H₂O)₂][Ni(bbimp)(H₂O)₂]₂·4H₂O (2)。化合物1是4，4′-联吡啶作为桥连配体的中性双核结构。化合物2含有1个中性的[Ni₂(bbimp)₂(H₂O)₂]双核分子与2个中性的[Ni(bbimp)(H₂O)₂]单核分子。双核分子单元中的2个Ni(Ⅱ)离子被2个膦酸氧桥连。在化合物2中，膦酸氧桥连的2个Ni(Ⅱ)离子之间存在铁磁性相互作用。     

超分子化合物[M(4，4′-bipy)2(H2O)4·(4，4′-bipy)2·(3，5-diaba)2·8H2O](M=Co，Ni，Cd)的合成及晶体结构

合成了3个超分子化合物[M(4，4′-bipy)₂(H₂O)₄]·(4，4′-bipy)₂·(3，5-diaba)₂·8H₂O(M=Co (1)，Ni (2)，Cd (3)；4，4′-bipy=4，4′-联吡啶；3，5-diaba=3，5-二氨基苯甲酸阴离子)，用红外光谱、元素分析及X-射线单晶衍射进行了表征。3个化合物的晶体都属于单斜晶系，空间群为P2/c。晶体学参数：化合物1：a=0.938 9(2) nm，b=0.775 1(1) nm，c=3.928 4(6) nm，β=90.14(2)°，V= 2.858 80(69) nm³，Z=4，D_c=1.397 g·cm^-3，F(000)=1 266，μ=0.380 mm^-1，R₁=0.034 9,wR₂=0.082 9;化合物2:a=0.938 3(2) nm,b=0.775 3(1) nm，c= 3.921 8(6) nm，β=90.09(1)°，V=2.852 80(68) nm³，Z=2，D_c=1.399 g·cm^-3，F(000)=1 268，μ=0.420 mm^-1，R₁=0.036 6，wR₂=0.080 5；化合物3：a=0.940 91(13) nm，b=0.778 85(11) nm，c=3.971 2(5) nm，β=90.10°，V=2.910 2(7) nm³，Z=2，D_c=1.433 g·cm^-3，F(000)=1 308，μ=0.454 mm^-1，R₁=0.046 8，wR₂=0.096 4。3，5-diaba未参与配位，在配位阳离子[M(4，4′-bipy)₂(H₂O)₄]²⁺中，金属离子M(II)与来自2个4，4′-bipy的2个氮原子和4个水分子的氧原子配位，呈八面体的几何构型。分子中还存在未配位的4，4′-bipy。通过配位阳离子、游离4，4′-bipy及未配位的3，5-diaba间的丰富氢键，构建成具有三维结构的超分子化合物。     

配位聚合物[Zn(3-aba)2]n·nH2O和[Cd(3-aba)2]n的合成与晶体结构

用水热法合成了2个新的配位聚合物[Zn(3-aba)₂]_n·nH₂O (1)和[Cd(3-aba)₂]_n (2)(3-aba=间氨基苯甲酸阴离子)，对它们进行 了元素分析、热分析、红外光谱和X射线单晶衍射等表征。配位聚合物1晶体属正交晶系，Pca2₁空间群，晶体学数据为：a=0.926 26(8) nm，b=1.600 73(15) nm，c=1.885 22(17) nm，β=90°，V=2.795 2(4) nm³，Z=4，μ=1.783 mm^-1，D_c=1.690 g·cm^-3，R₁=0.027 9，wR₂=0.064 8；配位聚合物2晶体属单斜晶系，P2₁/n空间群，晶体学数据为：a=0.900 68(7) nm，b=0.452 03(4) nm，c=1.568 02(12) nm，β=106.075 0(10)°，V=0.613 43(9) nm³，Z=1，μ=1.799 mm^-1，D_c=2.082 g·cm^-3，R₁=0.019 8，wR₂=0.055 8。在配合物1中，配体分子以双齿配位模式与锌离子配位，而在配合物2中，它以三齿配位模式与镉离子配位。2个配合物均具有二维网状结构。     

两个3d-4f杂核配合物[Fe(phen)3]2[FeLn(H2O)(tiron)3]·6H2O的合成、晶体结构和磁性(Ln=HoⅢ, YbⅢ)

Ln₂O₃、硝酸铁、邻菲罗啉和钛铁试剂(tiron)通过水热法自组装合成了2个异质同晶的3d-4f杂核配合物[Fe(phen)₃]₂[FeLn(H₂O)(tiron)₃]·6H₂O, 其中, Ln=Ho^Ⅲ (1)和Yb^Ⅲ (2)。X-射线单晶衍射分析表明, 晶体属立方晶系, P2₁3空间群。3个tiron^4-配体利用酚氧桥联Ln³⁺和Fe³⁺形成具有C₃对称性的[FeLn(H₂O)(tiron)₃]^6-异双核配位单元, 其中七配位的Ln³⁺呈现一种畸变的单帽反三棱柱配位构型。配阳离子[Fe(phen)₃]³⁺通过phen-phen之间的π-π相互作用和与配阴离子间的静电引力等作用组装成三维的超分子。在2~300 K温度范围内测试了配合物的变温磁化率, 结果表明, Ln(Ⅲ)-Fe(Ⅲ)之间存在反铁磁性相互作用。     

配位聚合物{[CoL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成、波谱表征和磁学性质

A new Schiff base complex， CoL(ClO₄)·3H₂O (1) {L represents condensed from equal molar ratio of sali-cylaldehyde and diethylenetriamine} was synthesized and characterized. Further， a new coordination polymer， {[CoL][Fe^ⅡFe^Ⅲ(ox)₃·1.5H₂O]}_∞ (2)， was synthesized and characterized， where ox^2-=oxalate. The results of the IR and M?ssbauer spectra of 2 revealed that the coordination polymer exists 2-D layer structure in the solid state， and anions layer was formed by [^ⅡFe^Ⅲ(ox)₃]^- unit. The magnetic properties of 2 have been measured and the results indicate that there is magnetic ordering in the low temperature， which may arise from intermolecular ferromagnetic interactions or spin canted effects.     

新的桥联二氨基镱(II)配合物[{Me2Si(NPh)2Yb(THF)2}(m3-Cl)(m4-Cl){Li(THF)}2]2·2THF的合成及结构

无水YbCl₃与等当量的Li₂Me₂Si(NPh)₂在四氢呋喃中反应，生成了相应的镱(III)氯化物1 [{Me₂Si(NPh)₂Yb}(m2-Cl)(TMEDA)]₂·3PhMe （TMEDA = 四甲基乙二胺）。原位形成的配合物1经Na-K合金还原，高产率地得到了一个新的、分子中有四个LiCl络合的桥联二氨基镱(II)配合物2 [{Me₂Si(NPh)₂Yb(THF)₂}(m3-Cl)(m4-Cl){Li(THF)}2]2·2THF。这两个配合物经过X-射线的结构表征证实均为二聚体。配合物1中两个镱原子经氯桥连接成一个扭曲的八面体。配合物2中两个[Me₂Si(NPh)₂Yb(THF)₂](m3-Cl)[Li(THF)]₂结构单元经两个m4-Cl原子连接成一个“椅式”骨架。     

蝎型铜配合物：Cu2[ μ-pz]2[HB(pz)3]2和Cu[B(pz)4]2的合成、结构及热分解动力学性质

本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu₂[ μ-pz]₂[HB(pz)₃]₂(1)和Cu[B(pz)₄]₂(2)(pz：吡唑(C₃H₄N₂))。运用元素分析、红外光谱对配合物进行了表征，并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明：配合物1的热分解反应分两步，配合物2的热分解反应一步进行。通过计算，配合物1热分解的第一步反应的可能机理为成核与生长，n=1/4；第二步反应的可能机理为化学反应。其非等温动力学方程分别为：dα/dT=A/β e^-E/RT·1/4(1-α)[-ln(1-α)]^-3和dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能分别是520.37 kJ·mol^-1和149.65 kJ·mol^-1；指前因子lnA分别是118.06 s^-1和28.10 s^-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为：dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能是111.41 kJ·mol^-1；指前因子lnA是21.20 s^-1。     

Crystal structures of phosphomolybdyl salts: Pb(MoO2)2(PO4)2 and Ba(MoO2)2(PO4)2

Crystal structures of Pb(MoO₂)₂(PO₄)₂ and Ba(MoO₂)₂(PO₄)₂ were determined. Both compounds contain the molybdyl group MoO₂. The monoclinic unit-cell parameters are a = 6.353(7), b = 12.289(4), c = 11.800 Å, β = 92°56(6), and Z = 4 for the lead salt and a = 6.383(8), b = 7.142(7), c = 9.953(8) Å, β = 95°46(8), and Z = 2 for the barium salt. $\text{P2}{}_1\text{c}$ is the common space group. The R values are respectively R = 0.027 and R = 0.031 for 1964 and 1714 independent reflections. The frameworks built up by a three-dimensional network of monophosphate PO₄ and molybdyl MoO₂ groups are similar, characterized mainly by corner-sharing PO₄ and MoO₆ polyhedra. Two oxygen atoms of each MoO₆ group are bonded to the molybdenum atom only as in other molybdyl salts.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Ba3 (VO4)2-K2 Ba(MoO4)2 and Pb3 (VO4)2-K2 Pb(MoO4)2 systems

Phase equilibria in the Ba₃(VO₄)₂-K₂Ba(MoO₄)₂ and Pb3(VO₄)₂-K₂Pb(MoO₄)₂ systems have been investigated. In the first system, a continuous series of substitutional solid solutions with the palmierite structure is formed, and in the second one, the polymorphic transition in lead orthovanadate at 100°C restricts the extent of the palmierite-type solid solution to 10–100 mol % K₂Pb(MoO₄)₂. Original Russian Text ? V.D. Zhuravlev, Yu.A. Velikodnyi, A.S. Vinogradova-Zhabrova, A.P. Tyutyunnik, V.G. Zubkov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1746–1748.     

Qualitative structure of (CO2)2 and (OCS)2

Molecular beam deflection studies on (CO₂)₂ and (OCS)₂ indicate that both these species are polar molecules. Structural implications of this are explored in light of previous studies of these systems.     

A novel three-dimensional malonate-bridged complex {[Cu4(4,4′- bpy)8(mal)2(H2O)4](ClO4)2(H2O)4(CH3OH)2}n

A novel malonate-bridged copper (II) compound of formula {[Cu₄(4,4′-bpy)₈(mal)₂(H₂O)₄](ClO₄)₂(H₂O)₄(CH₃OH)₂}_n (4,4′-bpy = 4,4′-bipyridine; mal = malonate dianion) has been prepared and structurally characterized by X-ray crystallography. This compound exhibits a novel three-dimensional network being composed of Cu-4,4′-bipyridine layers which are pillared by malonate bridge ligands. The copper(II) ions has two different coordination environment.     

Synthesis, molecular structure, and catalytic activity of borohydride complexes [(Me3Si)2NC(NPri)2]2Nd(BH4)2Li(thf)2 and [(Me3Si)2NC(NPri)2]2Sm(BH4)2Li(thf)2

The reactions of lanthanide tris(borohydrides) Ln(BH₄)₃(thf)₃ (Ln = Sm or Nd) with 2 equiv. of lithium N,N′-diisopropyl-N′-bis(trimethylsilyl)guanidinate in toluene produced the [(Me₃Si)₂NC(NPrⁱ)₂]Ln(BH₄)₂Li(thf)₂ complexes (Ln = Sm or Nd), which were isolated in 57 and 42% yields, respectively, by recrystallization from hexane. X-ray diffraction experiments and NMR and IR spectroscopic studies demonstrated that the reactions afford monomeric ate complexes, in which the lanthanide and lithium atoms are linked to each other by two bridging borohydride groups. The complexes exhibit catalytic activity in polymerization of methyl methacrylate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–445, March, 2007.     

Platinumolefin bond strength in Pt(PPh3)2(CH2CH2) and Pt(PPh3)2 {C(CN)2C(CN)2}

The enthalpy of the reaction: Pt(PPh₃)₂ (CH₂CH₂)(cryst.) + C(CN)₂C(CN)₂ (g) → Pt(PPh₃)₂ {C(CN)₂C(CN)₂}(cryst.) + CH₂ CH₂ (g) has been determined as ΔH₂₉₈=?155.8±8.0 kJ·mol^?1, from solution calorimetry. The interpretation, that the platinumethylene bond is much weaker than the platinumtetracyanoethylene bond, is contrary to conclusions drawn recently from electron emission spectroscopic studies, but in agreement with available structural data.     

A new three-dimensional cobalt phosphate: Co5(OH2)4(HPO4)2(PO4)2

A three-dimensional (3D) cobalt phosphate: Co₅(OH₂)₄(HPO₄)₂(PO₄)₂ (1), has been synthesized by hydrothermal reaction and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic techniques. The title compound is a template free cobalt phosphate. Compound 1 exhibits a complex net architecture based on edge- and corner-sharing of CoO₆ and PO₄ polyhedra. The magnetic susceptibility measurements indicated that the title compound obeys Curie-Weiss behavior down to a temperature of 17 K at which an antiferromagnetic phase transition occurs.     

Structural study of Mn2(CO)8[P(NMe2)3]2

An X-ray crystal structure determination for the bimetallic complex Mn₂(CO)₈-[P(NMe₂)₃]₂ reveals that the P(NMe₂)₃ ligands are trans to the Mn---Mn bond and the Mn---Mn bond distance is relatively long, 2.946(1) Å.