New polynuclear molecular ferromagnetic complex {Co3((η2-NH2)2C6H2Me2)2(μ-OOCCMe3)2(η1-OOCCMe3)2(η2-OOCCMe3)2(HOOCCMe3)2}{Co((η2-NH2)2C6H2Me2)2(η1-OOCCMe3)2}

Russian Chemical Bulletin -     

Synthesis,Characterization and Crystal Structure of (PhCH2)2Sn(S2CENt2) and (PhCH2)2Sn(S2CNC4H8)2

Two new dibenzyltin bisditiocarbamates(PhCH2)2 Sn(S2CNEt2)2(1) and (PhCH2)2 Sn(S2CNC4H8)2(2) were synthesized by the reaction of dibenzyltin dichloride with dithiocarbamates and characterized by elemental analysis ,IR,^1H NMR and MS spectra.The crystal structures were determined by X-ray single crystal diffraction analysis.In both complexes,the tin atom is six-coordinated in a distorted octahedral configuration.In the crystals of 1,the molecular packing in unit cell reveals that the two adjacent molecules are symmetrically linked to each other in dimers by two Sn S interactions of 0.3816nm.In the crystals of 2,the molecules are packed in the unit cell in one-dimensional chain structure linked by weaker intermolecular S S conmtacts.     

{Cu2(tacn)2[μ-(MeN)2C2O2]}[(MeNH)2C2O2](ClO4)2的合 成、结构及性质研究

合成了双核配合物{Cu2(tacn)2[μ-(MeN)2C2O2]}[(MeNH)2C2O2](ClO4)2(tacn=1,4,7-三氮杂环壬烷)。通过元素分析、红外光谱、ESR谱和电子光谱对配合物进行表征，并利用单晶X射线衍射法测定其结构，晶体属单斜晶系，空间群为P21/n,a=0.72572(16)nm,b=2.5616(6)nm,c=0.9128(2)nm,β=90.096(5)°，V=1.6969(7)nm^3,Dcald=1.590Mg.m^-^3,Z=2,F(000)=840,R1=0.0529,wR2=0.1341,Gof=1.028,△ρ=632～390e.nm^-^3。晶体由对称的双核Cu单元、中性草酰胺分子及高氯酸根堆积而成。两个铜原子配位数为五，处于变形四方锥的配位环境中。在5～300K范围内磁性测定表明：配合物中存在反铁磁偶合相互作用，经理论拟合：g=1.98,J=-219cm^-^1。     

[Mn2(TNR)2(CHZ)2(H2O)4]·2H2O的合成和晶体结构

将ＭｎＣＯ３与２,４,６－三硝基间苯二酚（斯蒂芬酸、ＴＮＲ）分散于蒸馏水中,加热搅拌制备出斯蒂酚酸锰溶液,再与碳酰肼（ＣＨＺ）水溶液反应制备〖Ｍｎ２（ＴＮＲ）２（ＣＨＺ）２（Ｈ２Ｏ）４〗·２Ｈ２Ｏ（Ｃ１４Ｈ２６Ｍｎ２Ｎ１４Ｏ２４,Ｍｒ＝８８４．３６）,并对其进行了元素分析和红外表征,利用单晶分析测定了晶体结构。该化合物为双核配合物,属三斜晶系,空间群为＾－Ｐ１,晶体学数据如下：ａ＝７．２８０（１）     

CRYSTAL STRUCTURE OF H(PyH)_3 [MO_2o_4 (C_2o_4)_2 (H_2o)_2)_2'2H_2o

<正> Introduction. The complexes of Mo(V) and oxalate are found to exist in several various configurations. As an anologous compound for the activecenter of Mo enzymes they have attracted broad attention. It was found by Sobczak and Ziolkowski in 1976 that these types of complexes had a higher catalytic selectivity in the epoxidation of olefine by hydroperoxides     

Crystal structure of Na2[(UO2)2(SeO4)3(H2O)2] · 6.5H2O

The compound Na₂[(UO₂)₂(SeO₄)₃(H₂O)₂] · 6.5H₂O (I) is studied using X-ray diffraction. The compound crystallizes in the monoclinic crystal system with the unit cell parameters a = 19.7366(8) Å, b = 10.8206(4) Å, c = 21.3577(8) Å, β = 103.4311(1)°, Z = 4, and the space group P2₁/c, R ₁ = 0.0379. Compound I is found to be a representative of the crystal-chemical group A₂T ₂ ³ B²M ₂ ¹ (A = UO ₂ ²⁺ ) of uranyl complexes and contains the cage group [(UO₂)₂(SeO₄)₃(H₂O)₂]^2?.     

[Pb2(TNR)2(CHZ)2(H2O)2]4H2O的结构及热分解机理

The coordination compound of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O was prepared by using the aqueous solution of carbohydrazide, lead nitrate and sodium styphnate. The molecular structure of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O(C 7H 13 N 7O 12 Pb, Mr=594.43) was determined by using a single crystal diffraction analysis .The thermal decomposition mechanism of the title compound was studied by TGDTG, DSC and IR techniques. The crystal belongs to monoclinic with space group P2 1/n.The unit cell parameters are as follows: a=0.64700(10)nm, b=1.6074(3)nm, c=1.4883(3)nm,β=97.42(2)°,V=1.5349(5)nm3, Z=2, DC=2.572g•cm -3 ,μ(Mo, Kα)=11.080cm -1 , F(000)=1128. R=0.0422, Rw=0.0735. The binuclear lead coordination compound is bridged by two carbohydrazide molecules. The molecule has a symmetrical center. TNR 2- ,CHZ and H 2O coordinate with the central ions simultaneously.     

CRYSTAL STRUCTURE OF Mo_2(u-S)_2(S_2P(OEt)_2)_4

<正> Mr=996.91, triclinic, P1, a=8.773(2), b=9.712(3), c=13.652(1) A; α=69.24(0), β=70.43(3), γ=66.87(l)°; Z=l, Dx=1.699 g/cm 3. Final R=0.053 for 3186 reflections with I≥3a(I). There is an interesting trans influence of μ-s bridge in this binuclear cluster. Mo-Mo distance is 2.752(1) A.     

2D氢键网络镉配合物Cd(pyridine-2-sulfonato)2(H2O)2和锌配合物Zn(pyridine-2-sulfonato)2(H2O)2的合成和晶体结构

合成了镉的吡啶-2-磺酸配合物Cd(C5H4NSO3)2(H2O)2 1和锌的吡啶-2-磺酸配合物Zn(C5H4NSO3)2(H2O)2 2。 研究表明, 2个化合物属异质同晶, 均属单斜晶系, 空间群为C2/c. 化合物1晶胞参数为:a = 13.7671(5), b = 7.2778(3), c = 16.1559(9) ? b = 106.656(3)? V = 1550.8(1) 3, Z = 4, Dc = 1.990 g/cm3, m =1.719 mm-1, F(000) = 920, R = 0.0225, wR = 0.0584, 共收集到1759个独立衍射点, 其中I≥2(I)的可观测点为1681个;化合物2晶胞参数为:a = 13.711(1), b = 7.1451(9), c = 15.972(1) , b =107.079(5)? V = 1495.7(3) 3, Z = 4, Dc = 1.855 g/cm3, m = 1.964 mm-1, F(000) = 848, R = 0.0310, wR = 0.0831, 共收集到1707个独立衍射点, 其中I≥2(I)的可观测点为1592个。在2个标题配合物中, Cd2+离子(或Zn2+离子)由2个吡啶-2-磺酸中的2个氮和2个氧以及2个水分子中的2个氧配位形成畸变的N2O4八面体配位构型。每个配合物分子具有晶体学2次旋转轴对称性。配合物分子之间通过许多OH(配位水分子)LO(未配位磺酸根)氢键联结成二维结构网络。     

CRYSTAL STRUCTURE OF (Ph_2Ppy)_2 (μ-Cl)_2Cu_2Cl_2

<正> (Ph2Ppy)2(μ-Cl)2Cu2Cl2 (C34H28Cl4Cu2N2P2): Mr=795.5, triclinic, Pl, a=13.891(2), b= 13.196(3), c= 20.158(4) A, d= 90.28(1)°, β=110.05(2)°, r= 90.13(1)°, Z=4, V= 3471.04A3, Dx=1.53 gcm-3, R=0.066, Rw= 0.076 for 5486 observed unique reflections. The complex was prepared by the reaction of (Ph2Ppy)2NiCl2 with CuC≡CPh in CH2Cl2 solution.     

[Pb2(TNR)2(CHZ)2(H2O)2]·4H2O的结构及热分解机理

用碳酰肼 (CHZ ,NH2 NHCONHNH2 )、硝酸铅和三硝基间苯二酚 (TNR ,斯蒂酚酸 )的水溶液制备 [Pb2 (TNR) 2 (CHZ) 2 (H2 O) 2 ]·4H2 O .采用单晶分析的方法测定它的分子结构 ,并用TG DTG、DSC和　IR相结合的技术研究它的热分解机理 .所得晶体属单斜晶系 ,P2 1/n空间群 .晶体学参数为 :a=0 .6470 0 ( 10 )nm ,b =1.60 74 ( 3)nm ,c=1.4 883( 3)nm ,β =97.4 2 ( 2 )° ,V =1.534 9( 5)n ,Z =2 ,DC=2 .572 g·cm- 3,μ(Mo ,Kα) =11.0 80cm- 1,F( 0 0 0 ) =112 8.最终偏离因子R =0 .0 4 2 2 ,Rw=0 .0 735.该配合物分子呈中心对称 ,两个羰基O原子形成两个氧桥 ,TNR2 - ,CHZ和H2 O同时参与了与中心离子的配位     

Synthesis, structure and reactivity of binuclear metal-metal bonded molybdenum(V) and tungsten(V) thioselenohalides: Molecular structure of Mo2(μ-S2)2Cl6(SeCl2)2 and W2(μ-S2)2Cl6(SeCl2)2

Thioselenohalide complexes Mo₂(μ-S₂)₂Cl₆(SeCl₂)₂ (I), Mo₂(μ-S₂)₂Br₆(SeBr₂)₂ (II), and W₂(μ-S₂)₂Br₆(SeBr₂)₂ (III) were synthesized by the reactions of corresponding metal halides or carbonyls or molybdenum metal with excesses of S₂ X ₂+Se₂ X ₂ mixtures. The complex W₂(μ-S₂)₂Cl₆(SeCl₂)₂ (IV) was obtained by an exchange reaction between (III) and excess of Se₂Cl₂. Coordination of the neutral SeX ₂ ligands to thiohalidesM ₂(μ-S₂)₂ X ₆ results in higher thermal stability, and suggests the possibility to synthesize SeX ₂ complexes of the unstable parent tungsten thiohalides. An unusual oxidative addition reaction of (I) was detected: {fx27-1} Both (I) and (IV) were characterized by X-ray crystal structure analysis. They are isostructural and form discrete molecules. Bridging S ₂ ^2? ligands are coordinated perpendicularly to the metal-metal bond;d(M?M)=2.8066 Å and 2.793 Å for I and IV, respectively. Nonequivalence of chlorine atoms which are bound to the metal atom, relate to nonequivalence of halogen atoms in the complexesM ₂(μ?S₂)₂ X ₈ ^2? . Chlorine atomstrans to SeCl₂ ligands form short bonds with the metal; the corresponding³⁵Cl NQR frequency is increased. The selenium dichloride ligand is ambidentate. The selenium atom binds as a donor to the metal and as an acceptor to two chlorine atoms which are also bound covalently to the same metal atom.     

Can Sn(OCH2CH2NMe2)2 behave as a stannylene? Equatorial-axial isomerism in the tin(II)-iron(0) complex (Me2NCH2CH2O)2Sn-Fe(CO)4

Equatorial-axial isomerism of the tin(II)-iron(0) complex (Me2NCH2CH2O)2Sn-Fe(CO)4 (), which indicates that the free Sn(OCH2CH2NMe2)2 () ligand can behave as a stannylene, has been revealed and studied by NMR and IR spectroscopy in solution as well as by Raman spectroscopy and X-ray diffraction analysis in the solid-state.     

Palladium(II) saccharinate complexes trans-[Pd(sac)2(LH)2] with amino- and acetylamino-pyridine co-ligands: molecular structures of trans-[PdCl2(2-ampyH)2].2dmf (2-ampyH = 2-amino-3-methylpyridine) and trans-[Pd(κ2-2-acmpy)2] (2-acmpyH = 2-acetylamino-3-methylpyridine)

Reaction of Na₂[PdCl₄] with two equivalents of amino- or acetylamino-pyridines (LH) affords trans-[PdCl₂-(LH)₂] {LH = 2-amino-3-methylpyridine (2-ampyH), 3-aminopyridine (3-apyH), 2-acetylamino-3-methylpyridine (2-acmpyH), 3-acetylamino-pyridine (3-acpyH)}. An X-ray crystal structure of trans-[PdCl₂(2-ampyH)₂] shows that the 2-ampy-H ligands are coordinated in a monodentate fashion via the nitrogen atoms of the pyridine rings. Treatment of trans-[PdCl₂(2-acmpyH)₂] with NEt₃ affords the cyclometalated complex, trans-[Pd(κ²-2-acmpy)₂], the X-ray structure of which shows that the 2-acmpy ligand is coordinated to palladium in a bidentate fashion via the nitrogen atom of the pyridine ring and oxygen. Reaction of trans-[PdCl₂(LH)₂] with two equivalents of sodium saccharinate affords the bis(saccharinate) complexes, trans-[Pd(sac)₂(LH)₂], in which the saccharinate anions are coordinated via the amide nitrogen atom.     

Complexes [Ni2(μ-OH2)(μ-O2CCH(CH3)2)2L2–4((CH3)2CHCO2)2]: Synthesis,Structure, and Mass Spectrometric Studies

Russian Journal of Coordination Chemistry - Three new binuclear aqua-bridged nickel(II) 2-methylpropionate complexes [Ni2(μ-OH2)(μ-O2CCH(CH3)2)2L2–4((CH3)2CHCO2)2] (L is...     

Synthesis of Palladium Clusters with the P--N--P Assembling Ligands (Ph2P)2CH2 (dppm) and (Ph2P)2NH (dppa). Crystal Structure of [Pd4(μ-Cl)2(μ-dppm)2(μ-dppa)2](PF6)2

Tetrapalladium clusters containing dppa or dppa and dppm bridging ligands were prepared by condensation of dinuclear units. Reaction of [Pd₂Cl₂(-dppa)₂] with [Cu(PPh₃)]PF₆ (generated in situ in THF) yielded [Pd₄(-Cl)₂(-dppa)₄] (PF₆)₂ (4) in a virtually quantitative yield but [Pd₄(-Cl)₂(-dppm)₂(-dppa)₂] (PF₆)₂ (6) was best prepared in CH₂Cl₂ from [Pd₂Cl₂(-dppm)₂] and [Pd₂(MeCN)₂(-dppa)₂](PF₆)₂ (2). The structure of 6·2(CH₃)₂CO·2H₂O was determined by X-ray diffraction. It consists of a planar, centrosymmetric 10-membered ring structure. The four bridging diphosphine ligands are of two types: two dppa ligands support the Pd Pd bonds [2.6055(4) Å], whereas the two dppm ligands bridge between two palladium atoms separated by 3.722(4) Å, which are also bridged by a chloride ligand.     

(CH2 )2 (C9 H6 )2 YbN(SiMe3 )2 的合成与催化活性研究

用1,2-二茚基乙烷[(CH2)2(C9H7)2]与四配位的三[三甲基硅基胺基]镱的络合物{[(Me3Si)2N]3Yb(Ⅲ)(μ-Cl)Li(THF),}反应,生成桥联二茚基镱的胺基配合物[(CH2)2(C9H6)2YbN(SiMe3)2],其结构经^1HNMR,IR,XFD),GPC和元素分析表征,并初步研究了其对甲基丙烯酸甲酯聚合反应的催化活性。