配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

多硫二硫烯铜配合物(n-Bu4N)[Cu(cddt)2]和(Ph4P)[Cu(cddt)2]的合成、表征及其结构

Two copper complexes with a new multi-sulfur 1,2-dithiolene ligand, C[Cu(cddt)₂] (C=tetrabutylammoni-um, n-Bu₄N⁺; tetraphenylphosphonium, Ph₄P⁺; cddt = 4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3 dithi-olate) have been synthesized and characterized by electrochemical studies, IR, EA, etc. The structure of (Ph₄P)[Cu(cddt)₂] was determined by single crystal X-ray analysis. The complex was crystallized in the triclinic, space group P1 with the cell dimensions a=10.460(2)?, b=13.000(3)?,c=16.270(3)?, α=86.68(3)°,β= 71.92(3)°,γ=66.66(3)° and Z=2. R₁=0.0548, wR₂=0.1358 for 6786 independent reflections. The four S atoms surround the Cu atom [CuS₄] core is a square-planar environment.     

[Cu(Hsal)2(py)2]n晶体结构和二维堆积网络

０引言水杨酸具有羧基和羟基，是双功能基配体，羧基和羟基可分别脱去氢，因此有多种形式可参与配位（见Scheme１），其中Hsal－１的形式仅见一例报道犤１犦，其可靠性有待更多的研究来确证。对铜／水杨酸／吡啶三元体系的研究已有多篇文献报道犤２～４犦，亦有几种化合物合成，例如Cu（Hsal）２（py）２和Cu（sal）（py）２等。配合物Cu（sal）（py）２的可靠性值得怀疑，原文中无合成和表征犤３犦。铜／水杨酸／吡啶衍生物三元体系已有多个晶体结构报道犤５，６犦，但迄今无铜／水杨酸／吡啶三元体系晶体结构报道。对于配合物Cu（Hsal…     

[(C5H4Me)2Sm(THF)(DME)][BPh4]的合成和晶体结构

三(甲基环戊二烯基)钐和四苯基硼银在四氢呋喃和乙二醇二甲醚混合溶剂中反应合成了阳离子稀土有机化合物[(C     

降冰片二烯衍生物的光异构化 Ⅱ.2-萘胺甲酰基-2,5-[2.2.1]-双环庚二烯的光异构化

合成了降冰片二烯衍生物——2-萘胺甲酰基-2,5-[2.2.1]-双环庚二烯(B)。研究了它在太阳光直接照射下的光异构化反应。(?) 此外,还确定了化合物(B)和(C)的分子结构。它们都是文献中未曾报道过的新化合物。     

2,5-二氢氧杂环庚三烯合成方法研究进展*

2,5-二氢氧杂环庚三烯是许多天然产物和生物活性分子的骨架结构,实现该类化合物的高效合成一直是有机化学家的研究热点。与五元和六元环化合物合成方法相比,2,5-二氢氧杂环庚三烯的合成更具挑战性。本文综述了近年来利用烯烃复分解关环法、过渡金属催化偶联法、retro-Claisen重排法以及一些其他方法合成2,5-二氢氧杂环庚三烯的研究进展。     

双核Fe配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2的合成和晶体结构

由侧链带有噻吩的环戊二烯基配体C5H5C6H10C4H3S与Fe(CO)5在二甲苯中加热回流,合成了1个新颖的四羰基二铁配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2。通过元素分析、IR、1H NMR对其结构进行了表征,用X-射线单晶衍射确定了其结构。X-射线单晶衍射表明配合物中有2个桥羰基和2个端羰基,Fe-Fe的键长为0.25465(10)nm。     

[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.     

Some transesterification reactions of [Ir(CO2Me)(CO)2(PPh3)2]

The iridium(I) complex [Ir(CO₂Me)(CO)₂(PPh₃)₂] undergoes a transesterification reaction with the alcohols CH₂C(R)CH₂OH (R = H, Me), MeCCCH₂CH₂OH, and HOCH₂CH₂OH to afford the complexes

[Ir(CO₂CH₂CH₂CMe)(CO)₂(PPh₃)₂] and [Ir(CO₂CH₂CH₂OH)(CO)₂(PPh₃)₂], respectively. In contrast the acetylenic alcohol HCCCH₂CH₂OH gives [Ir(CCCH₂CH₂OH)(CO)PPh₃)₂]. Some reactions of the new complexes are described.     

Re4(CO)12[μ3-InRe(CO)5]4 und Re2(CO)8[μ-InRe(CO)5]2-cluster aus dem reaktionssystem In/Re2(CO)10 in xylol

The thermally stable solids Re₂(CO)₈[μ-InRe(CO)₅]₂ and Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ could be obtained by treatment of In with Re₂(CO)₁₀ in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re₂(CO)₈[μ-InRe(CO)₅]₂, Re₄(CO)₁₂[μ₃_InRe(CO)₅]₄ shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re₄(CO)₁₂-[μ₃-InRe(CO)₅]₄ dissolves monomerically in acetone, where as Re₂(CO)₈[μ-InRe(CO)₅]₂ dissociates yielding Re(CO)₅^? anions. Single-crystal X-ray analyses of Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ establish the metal skeleton. The central molecular fragment Re₄(CO)₁₂ contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ₃-InRe(CO)₅ group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re₄ tetrahedron and the metal skeleton was realized for the first time. By treating Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ with Br₂ the existence of Re(CO)₅ ligands could be proved by isolating BrRe(CO)₅.     

2-巯甲基噻吩与[Mn2(CO)10]原子簇化合物反应生成[MnS(CO)3]4及结构表征(英)

The compound [Mn₂(CO)₁₀] reacts with 2-(Methylthio)thiophene (C₅H₆S₂) while refluxing in xylene to afford a methylthio-tetramanganese product [MnS(CO)₃]₄, in which C₅H₆S₂ is cleaved with loss of thiophene. The crystal structure of [MnS(CO)₃]₄ has been studied by direct method. Based on the 21 685 unique reflections collected using MoKα of X-ray radiation and a CCD-based detector, it is refined to an agreement index (R₁) of 0.079 0. The cell is triclinic with dimensions: a=1.719 49 nm, b=1.959 2 nm, c=2.632 6 nm and α=79.733°, β=71.407°, γ=89.387°. There are 12 unit cells of [MnS(CO)₃]₄ in the cell, with space group P1.     

Reactions of isonitriles with [Fe3(CO)12] and [Ru3(CO)12] monitored by electrospray mass spectrometry: structural characterisation of [Fe3(CO)10(CNPh)2] and [Ru4(CO)11(μ3-η-CNPh)2(CNPh)]

The reactions of [Fe₃(CO)₁₂] or [Ru₃(CO)₁₂] with RNC (R=Ph, C₆H₄OMe-p or CH₂SO₂C₆H₄Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe₃(CO)₁₂], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe₃(CO)₁₀(CNPh)₂] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru₃(CO)₁₂] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru₄(CO)₁₁(CNPh)₃] was structurally characterised and has a spiked-triangular Ru₄ core with two of the CNPh ligands coordinated in an unusual μ₃-η² mode.     

Dual luminescences in [W(Cp)(CO)3]2 and [Mo(Cp)(CO)3]2

Cyclohexane solutions of [W(Cp)(CO)₃]₂ and [Mo(Cp)(CO)₃]₂ exhibit weak bimodal emission spectra when excited With 354 nm picosecond pulses, but do not luminesce when pumped at 530 nm. Picosecond lifetimes characterize the short-wavelength, emission bands, which may originate from metal-cyclopentadienyl CT excited states.     

[Cu(HIm)2(PPh3)2](BF4)的合成与晶体结构

A Cu(Ⅰ) complex with mix ligands [Cu(HIm)₂(PPh₃)₂](BF₄) was synthesized and characterized by elemental analysis, IRspectroscopy and X-ray diffraction crystallography. The crystal belongs to monoclinic system and P2₁/c space group, with cell parameters, a=1.2836(3)nm, b=1.5089(3)nm, c=2.0661(4)nm, α=90°, β=101.464(4)°,γ=90°, V=3.9219(13)nm³, Z=4 and D_c=1.374mg·m^-3. The Cu(Ⅰ) is coordinated by two Patoms from triphenylphosphine and two Natoms from imidazole to form the distorted tetrahedral geometry.     

Stabilisation of [Fe2(CO)9] and [Ru2(CO)9] bu substitution with bridging diphosphorus ligands

Reaction of [Fe₂(CO)₉] with a half molar amount of R₂PYPR₂ (Y = CH₂, R = Ph, Me, OMe or OPrⁱ; Y = N(Et), R = OPh, OMe or OCH₂; Y = N(Me), R = OPrⁱ or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe₂(μ-CO)(CO)₆{μ-R₂PYPR₂}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe₂(μ-CO)(C))₄{μ-R₂PYPR₂}₂] but under thermal conditions in the formation of the mononuclear species [Fe(CO)₃{R₂PYPR₂}]. Reaction of [Ru₃(CO)₁₂] with an equimolar amount of (RO)₂PN(R′)P(OR)₂ (R′ = Me, R = Prⁱ or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru₃(CO)₁₀{μ-(RO)₂PN(OR)₂}] which reacts further with excess (RO)₂PN(R′)P(OR)₂ on irradiation with ultraviolet light to afford the dinuclear compound [Ru₂(μ-CO)(CO₄{μ-(RO)₂PN(R′)P(OR)₂}₂]. The molecular structure of [Ru₂(μ-CO)(CO)₄{μ-(MeO)₂PN(Et)P(OMe)₂}₂], which has been determined by X-ray crystallography, is described.     

The standard enthalpies of formation of (ClOF2)2[MnF6] and ClOF2[BF4] crystals

The enthalpies of interaction of (ClOF₂)₂[MnF₆](cr) and ClOF₂[BF₄](cr) with water and an aqueous solution of alkali and the enthalpies of several auxiliary processes were measured at 298.15 K on an isothermic-shell calorimeter. Based on these and literature data, the standard enthalpies of formation of (ClOF₂)₂[MnF₆](cr) and ClOF₂[BF₄](cr) at 298.15 K were calculated by two independent methods (−1643 ± 11 and −1368 ± 5 kJ/mol, respectively). Original Russian Text ? A.A. Firer, S.N. Solov’ev, A.Ya. Dupal, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 7, pp. 1391–1393.