[M(en)3]2Sn2Se6(M=Mn,Zn)的制备及其热稳定性

用有机溶剂热生长技术(SolvothermalTechnique)制备过渡金属锰和锌硒化物[Mn(en)3]2Sn2Se6(Ⅰ),[Zn(en)3]2Sn2Se6(Ⅱ).用单晶X射线衍射技术对其进行晶体结构分析.[Zn(en)3]2Sn2Se6样品的热分析结果表明,该化合物的热分解分三步进行.光学性质测试表明它们是半导体材料,[Mn(en)3]2Sn2Se6的能带隙为1.76eV.[Zn(en)3]2Sn2Se6的能带隙为2.49eV.     

Synthesis and characterization of one-dimensional coordination polymers, [M(sac)2(μ–pyz)(H2O)2] n [M=ZnII,CdII, pyz = pyrazine,and sac = saccharinate]

Two new coordination polymers, [M(sac)₂(μ–pyz)(H₂O)₂] _n [M=Zn^II(1), Cd^II(2), pyz =?pyrazine, and sac =?saccharinate], have been prepared and characterized by elemental analysis, FTIR spectroscopy, thermal analysis and single crystal X-ray diffraction. Both complexes are isomorphous and crystallize in the triclinic P 1 space group. The metal(II) ions are octahedrally coordinated by two sac, two aqua and two pyz ligands. The sac ligands are N-coordinated, while the pyz ligands are bridges between the metal centers, leading to one-dimensional linear chains. Intra-chain M–M separations in 1 and 2 are 7.218 and 7.498 Å, respectively. The individual chains are linked by strong OW–H ··· O(sac) hydrogen bonds into two–dimensional layers, which are further assembled into three–dimensional supramolecular networks by aromatic π(sac) ··· π(sac) stackings interactions.     

金属有机自由基离子盐[Fe(CpMe)2][M(dmit)2]和[FeCp(Tol)]n[M(dmit)2]的合成和固体导电性质

报道了6个新的含均同或混合茂铁阳离子和[M(dmit)₂]阴离子的金属有机自由基离子盐类化合物[Fe(CpMe)₂]IM(dmit)₂]和[FeCp(Tol)],[M(dmit)₂]的合成和鉴定,测定了化合物的电导率,讨论了化合物的结构对电导率的影响,发现[Fe(CpMe)₂][M(dmit)₂]的室温电导率比相应的[M(mnt)₂]阴离子盐要高37个数量级.     

Homoleptic diphosphacyclobutadiene complexes [M(η(4)-P2C2R2)2]x- (M = Fe, Co; x = 0, 1)

The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)(thf)(2)][Fe(η(4)-P(2)C(2)tBu(2))(2)] (K1), [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)tBu(2))(2)] (K2), and [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)Ad(2))(2)] (K3, Ad = adamantyl) were obtained from reactions of [K([18]crown-6)(thf)(2)][M(η(4)-C(14)H(10))(2)] (M = Fe, Co) with tBuC[triple bond]P (1, 2), or with AdC[triple bond]P (3). Neutral sandwiches [M(η(4)-P(2)C(2)tBu(2))(2)] (4: M = Fe 5: M = Co) were obtained by oxidizing 1 and 2 with [Cp(2)Fe]PF(6). Cyclic voltammetry and spectro-electrochemistry indicate that the two [M(η(4)-P(2)C(2)tBu(2))(2)](-)/[M(η(4)-P(2)C(2)tBu(2))(2)] moieties can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1-5 were characterized by multinuclear NMR, EPR (1 and 5), UV/Vis, and M?ssbauer spectroscopies (1 and 4), mass spectrometry (4 and 5), and microanalysis (1-3). The molecular structures of 1-5 were determined by using X-ray crystallography. Essentially D(2d)-symmetric structures were found for all five complexes, which show the two 1,3-diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal-ligand π bonding in 1-5. Possible oxidation state assignments for the metal ions are discussed.     

Electrophilic Substitution Mn(II) → M(II) (M = Co,Ni, Cu,Zn, Cd) in Gelatin-Immobilized Mn2[Fe(CN)6]

Reactions of electrophilic substitution Mn(II) M(II) (M = Co, Ni, Cu, Zn, Cd) are studied in gelatin-immobilized Mn(II) hexacyanoferrate(II) systems brought in contact with aqueous solutions of metal chlorides MCl₂. As the result of this contact, Mn(II) is replaced by Co(II), Ni(II), Cu(II), Zn(II), or Cd(II) to give heteronuclear metal hexacyanoferrates(II) (MHCF) of Mn(II) and two-charged ions. Neither of the systems under study showed a complete substitution of Mn(II) or the formation of the respective mononuclear hexacyanoferrate(II) M₂[Fe(CN)₆]. When any of the above gelatin-immobilized MHCF was brought in contact with an aqueous solution of MnCl₂, no electrophilic substitution M(II) Mn(II) was observed even for a long contact time.     

Synthesis and characterisation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)-stannate]2−, [Q]2[Sn(dmit)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(dmio)3] and [tris(1,3-dithiole-2-thione-4,5-selenolato)stannate]2−, [Q]2[Sn(dsit)3], complexes: Analysis of the structural variations of the [Sn(dmit)3]2− and [Sn(dmio)3]2− dianions

[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₅)₃], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₄O)₃], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate]²⁻ [Q]₂[Sn(C₃S₃Se₂)₃], complexes, have been synthesised and characterised. Crystal structure determinations of [Q]₂[Sn(C₃S₅)₃] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe₄, NEt₄, and PPh₄) and [NEt₄]₂[Sn(C₃S₄O)₃] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe₄, in chains for the somewhat larger cation, NEt₄ and is absent for the still larger, PPh₄ cation.     

As-5、[As5M]-、[As5MAs5]2- (M=Ti,Zr, Hf)的结构和芳香性

用密度泛函理论(DFT)研究了As-5、[As5M]-和[As5MAs5]2- (M=Ti, Zr, Hf)的结构、频率、能量以及芳香性, 详细讨论了体系中不同类型的键和电子如化学键、孤对电子、核电子等对总的核独立化学位移(NICS)的影响. 结果表明, As-5、[As5M]-和[As5MAs5]2-的基态结构分别具有D5h、C5v和D5h对称性, 而且都具有芳香性. As-5 (D5h)的芳香性主要来源于As—As π键和As—As σ键的作用. [As5M]-(C5v)中各种As—M键的NICS分割值占主要优势, 其次是As—As之间形成的σ键. [As5TiAs5]2-(D5h)中, As—As π键的作用占主要优势. [As5ZrAs5]2-(D5h)中, As—As π键对体系总的NICS贡献相对减小, 而As—Zr键的作用增强. [As5HfAs5]2-(D5h)的芳香性主要来自As—Hf键的作用.     

[M(dap)3]2(Sb2Se5)·xH2O(M=Ni,x=2;M=Zn,x=0)的溶剂热合成及晶体结构

利用溶剂热法合成了2种新的有机杂化锑硒化合物[Ni(dap)3]2(Sb2Se5)].2H2O(1)和[Zn(dap)3]2(Sb2Se5)](2)(dap=1,2-丙二胺),单晶X射线衍射分析结果表明,1属于三方晶系,P3121空间群,晶胞参数为a=10.7574(14),b=10.7574(14),c=31.672(4),γ=120.00°,z=4。2属于单斜晶系,P21空间群,晶胞参数为a=10.772(2),b=16.391(3),c=11.704(2),β=100.912(4)°,z=4。在2种化合物中,Ni2 与Zn2 离子分别与3个dap配体螯合形成畸变八面体几何构型,其中dap配体的N原子是无序的,而二聚[Sb2Se5]2-阴离子是由2个SbSe3三角锥共用1个Se原子连接而成。     

Electrophilic Substitution Co(II)→M(II) (M = Mn,Ni, Cu,Zn, Cd) in Co2[Fe(CN)6] Gelatin-Immobilized Matrices

Electrophilic substitutions Co(II) M(II) (M = Mn, Ni, Cu, Zn, Cd) in cobalt(II) hexacyanoferrate(II) gelatin-immobilized matrices in contact with aqueous solutions of corresponding chlorides MCl₂ were studied. As a result of this contact, Co(II) was shown to be replaced to some extent by Ni(II), Cu(II), Zn(II), or Cd(II) and to give heteronuclear cobalt(II) hexacyanoferrates(II) and two-charge ions. A complete substitution of Co(II) or the formation the respective mononuclear hexacyanoferrate(II) M₂[Fe(CN)₂] was observed in neither of the studied systems Co(II) M(II). No Co(II) Mn(II) substitution was observed, even though the immobilized matrix was in contact with a solution for a long time.     

2-[Pyridin-2(4)-yl]-N-[ω-vinyloxyalkyl]ethanamines

Russian Journal of Organic Chemistry -     

Two isotypic transition metal germanophosphates M(II)4(H2O)4[Ge(OH)2(HPO4)2(PO4)2] (M(II) = Fe, Co): synthesis, structure, Mössbauer spectroscopy, and magnetic properties

Synthetic, structural, thermogravimetric, M?ssbauer spectroscopic, and magnetic studies were performed on two new isotypic germanophosphates, M(II)(4)(H(2)O)(4)[Ge(OH)(2)(HPO(4))(2)(PO(4))(2)] (M(II) = Fe, Co), which have been prepared under hydro-/solvo-thermal conditions. Their crystal structures, determined from single crystal data, are built from zigzag chains of M(II)O(6)-octahedra sharing either trans or skew edges interconnected by [GeP(4)O(14)(OH)(4)](8-) germanophosphate pentamers to form three-dimensional neutral framework structure. The edge-sharing M(II)O(6)-octahedral chains lead to interesting magnetic properties. These two germanophosphates exhibit a paramagnetic to antiferromagnetic transition at low temperatures. Additionally, two antiferromagnetic ordering transitions at around 8 and 6 K were observed for cobalt compound while only one at 19 K for the iron compound. Low-dimensional magnetic correlations within the octahedral chains are also observed. The divalent state of Fe in the iron compound determined from the M?ssbauer study and the isothermal magnetization as well as thermal analyses are discussed.     

[Bu4N]2[Fe2(μ-S2O3)2(NO)4]: Synthesis,Structure, Redox Properties,and EPR Study

The [n-Bu₄N]₂[Fe₂(-S₂O₃)₂(NO)₄] complex was studied using X-ray diffraction analysis, cyclic voltammetry, and EPR spectroscopy, and its crystal structure was determined. The redox properties of the [Fe₂(-S₂O₃)₂(NO)₄]^2–anion in CH₃CN and CH₂Cl₂solutions were studied. An addition of excess reducer (sodium thiosulfate) to the thiosulfate complex was shown to produce an EPR signal with g= 2.03 typical of the mononuclear iron dinitrosyl complexes. The mechanism for [Fe₂(-S₂O₃)₂(NO)₄]^2–reduction was suggested.     

Cyanido-bridged one-dimensional systems assembled from [ReIVCl4(CN)2]2? and [MII(cyclam)]2+ (M = Ni, Cu) precursors

Three new cyanido-bridged heterometallic Re^IVNi^II and Re^IVCu^II one-dimensional systems were synthesized and extensively characterized both structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that these compounds display a common topology, with chains composed of alternating [Re^IVCl₄(CN)₂]^2? and [M^II(cyclam)]²⁺ (M = Ni in 1, Cu in 2) or [Cu^II(N,N??-dimethylcyclam)]²⁺ (in 3) building units. Two different chain orientations with a tilt angle of ca. 51° to 55° are present in the crystal packing of these compounds. The magnetic susceptibility measurements suggest the presence of intrachain ferromagnetic interactions between the S = 3/2 Re^IV centers and the 3d metal ions: S = 1 Ni^II or S = 1/2 Cu^II. At low temperature, a three-dimensional ordered magnetic phase induced by interchain antiferromagnetic interactions (antiferromagnetic for 1 and 2; canted antiferromagnetic for 3) is detected for the three compounds.     

四氮杂大环镍与[M(dmit)_2]~(2-)的离子对配合物[NiL][M(dmit)_2]的合成与表征

以1,3-二硫杂环戊烯-4,5-二硫醇-2-硫酮(dmit)和5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四-1,8-二烯(hmtade)或5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷(hmta)为配体合成了4个双金属的离子对配合物[NiL][M(dmit)2](L=hmtade,M=Ni(1);L=hmta,M=Ni(2);L=hmtade,M=Hg(3);L=hmta,M=Hg(4))。用元素分析、红外光谱、核磁共振氢谱、紫外-可见光谱、热重分析和循环伏安法等对它们进行了表征。研究结果表明,大环配体hmta、hmtade和配体dmit之间形成了N-H…S氢键,配阳离子均为五配位,配阴离子[M(dmit)2]2-的S对配阳离子的Ni(II)进行了配位。离子对配合物的稳定性顺序为:2134。     

[Ni(cien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

硫氰酸根的结构为N三C-S-,其两端的N原子和S原子分别有一对和三对孤对电子,因此,硫氰酸根可采用多种不同的配位模式与金属离子发生配位.硫氰酸根可作为单齿配体与一个金属离子配位,形成M-SCN或M-NCS的单核配合物,也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物[1-3];另一方面,硫氰酸根是一个具有一定共轭性的偶极子,可传递磁相作用.因此,选择硫氰酸根作为桥联配体,将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子,并研究它们的磁性已成为分子磁学的一个研究领域[4-6].本文仅报道标题配合物的合成与晶体结构.     

The reactions of [MI2(CO)3(NCMe)2] (M = Mo or W) with one equivalent of L (L = pyridine or substituted pyridines) to give [WI2(CO)3(NCMe)L] and [M(μ-I)I(CO)3L]2

The complexes [MI₂(CO)₃(NCMe)₂] (M = Mo or W) react with one equivalent of L in CH₂Cl₂ at room temperature to give initially the mononuclear seven-coordinate complexes [MI₂(CO)₃(NCMe)L] which have been isolated for M = W; L = 3Cl-py, 3Br-py, 4Cl-py and 4Br-py. These compounds dimerise to give the iodidebridged dimers [M(μ-I)I(CO)₃L]₂ by displacement of acetonitrile. When M = Mo; L = 3Cl-py, 3Br-py, 4Cl-py and 4Br-py, and when M = Mo and W; L = py, 2Me-py (for M = W only), 4Me-py, 3,5-Me₂-py, 2Cl-py and 2Br-py, only the dimeric complexes have been isolated. The ease of dimerisation of [MI₂(CO)₃(NCMe)L] is discussed in terms of the steric and electronic effects of the substituted pyridines.     

SYNTHESIS AND CRYSTAL STRUCTURE OF BIS (TETRAETHYLAMMONIUM) BIS[μ-(l,2-DITHIOETHELENE)-S,S']-BIS[l,2-DITHIOETHELENE-S,S']-DI-IRON(Ⅲ)

<正> INTRODUCTION. In our attempts of chemical simulation of the active center of nitrogenase we have been interested in the reaction system of various ferrous thiolates with thiomolybdatee. In previous papers, we have reported the syntheses of ferrous monodentothiolates and their reactions with tetrathiomolybdate. The possible structure type of ferrous thiolates when bidentothiols are used inspired our interest in this work.