CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_3 (μ-C_2H_5COO)(dtp)_3Py

<正> C20H40Mo3NO8P3S10, Mr=1123.93, triclinic, P1,a=12.972(3), b=13.763(2), c= 14.515(7)A,α=66.22(3),β=101.72(3),γ=118.90(1)° , V= 2076(2) A3, Z=2,Dc=1.798 g.cm-3, MoKa radiation, final R= 0.040 and Rw=0.056 for 5645 observed reflections. The molecule contains three Mo atoms arranged in a triangle with one capping-S atom, three (μ-S) atoms, one (μ-EtCOO) ligand, one chelate ligand dtp on each Mo atom, and one terminal Py on atom Mo(1). The coordination of Mo atoms is of distorted octahedron.     

Crystal structure of octabutyl-μ-dichloro-μ3-dioxodichlorotetratin(IV)

An X-ray diffraction study has shown that Sn atoms in octabutyl-μ-dichloro-μ₃-dioxodichlorotetratin(IV) have distorted trigonal bipyramidal geometry with cis-equatorial butyl groups. Sn(1)C(but) and Sn(2)C(but) bonds are 2.077(21), 2.111(26) and 2.097(23), 2.114(22) Å, respectively. The distances of the triply-bridging O atom from Sn atoms are 2.151(9), 2.018(9) and 2.069(9) Å, and those of the bridging Cl atom are 2.666(5) and 2.831(6) Å. The distance Cl(term)Sn(2) is 2.426(5) Å. Refinement of the structure, based on 1828 observed reflections, converged to an R factor of 0.049 and a weighted R of 0.053. Crystal data for the compound are: a 13.672(6), b 19.529(9), c 8.999(2) Å, β 102.66(3) °, space group P2₁/c, Z = 2, M_r = 1105.49 for [Sn₄(C₄H₉)₈Cl₄O₂], V 2344(2) ų, D_x 1.464 gcm⁻³, F(000) = 1096, λ(Mo-K_α) 0.71069 Å,μ 22.1 cm⁻¹ and T 293 K.     

Crystal structure of [Pd3(μ-OH)(μ-CH3COO)5]

The crystals of the [Pd₃(μ-OH)(μ-CH₃COO)₅] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure (a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) ų, space group Pna2₁, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd₃(μ-OH)(μ-CH₃COO)₅], in which the OH^? group, together with five CH₃COO^? anions, is a bridge ligand.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-O)-(μ-S)_3(μ-OOCCH_3)(dtp)_3(Py)

<正> The title compound was obtained by the reaction of Mo3(μ3-O) (μ-S)3(dtp)4(H2O) with CH3COONa and pyridine. Mo3C19H38N1O9P3S9,Mr= 1093. 79, triclinic, space group P1, a = 12. 921(3) , b = 14. 260(3) , c= 12. 800(3)(?),α = 97. 54(2), β=116. 66(1), γ=100. 10(2) °, V = 2015, 2(8)(?)3, Z=2, Dc = 1. 80gcm-3, F(000) = 1092, final R = 0. 066 for 3444 observations, room temp. In the structure the three Mo atoms form an isosceles triangle capped by a μ3-O atom with three sides of 2. 589(2) , 2. 642(2), and 2. 627(2) (?) respectively, and the car-boxyl bridged Mo-Mo bond is the shortest one.     

Poly­[copper(II)-μ-pyrazine-μ3-squarato]

In the structure of the title compound, [Cu(C₄O₄)(C₄H₄N₂)]_n, each copper cation is surrounded by three squarate (3,4-di­hydroxy-3-cyclo­butene-1,2-dioate) anions and two pyrazine ligands, all of which are located in special positions. The copper cation and all atoms of the squarate anion are located on a mirror plane, whereas the pyrazine ligand is located around a mirror plane which is perpendicular to the ring plane. The cations are connected via the squarate anions and the pyrazine ligands, forming sheets parallel to (001).     

Further studies of M3(μ3-O)(μ-X)3(μ-O2CCH3)3L3 (M=Mo,W) type clusters with nine core electrons

Four new compounds having nine cluster electrons and cores of the types Mo₃OCl₃, Mo₃OBr₃, and W₃OCl₃ are reported. Compound (1) prepared by reduction of [Bu₄N][Mo₃OCl₆(OAc)₃] in THF with metallic zinc, was shown by X-ray crystallography to be Mo₃OCl₄(OAc)₃ (THF)₂ (1). It forms crystals in space groupP2₁ with unit cell dimensionsa=9.472(2) Å,b=13.546(4) Å,c=9.652(2) Å, =101.70(2)°,V=1201(1) Å₃,Z=2. The [Mo₃(₃-O)(-Cl)₃]⁴⁺ core is surrounded by three -O₂CCH₃ anions, one Cl^–, and two THF and has Mo-Mo distances of 2.620(1) Å, 2.613(1) Å, and 2.530(1) Å, with the shortest bond between the two Mo atoms to which the THF molecules are coordinated. Compounds [Bu₄N]₂ [Mo₃OBr₆(O₂CCH₃)₃] · Me₂CO, (2) and [Mo₃OBr₃(O₂CCH₃)₃(PMe₃)₃]₃ · BF₄, (3) are the first two nine-electron Mo₃ species with a [Mo₃(₃-O) Br₃]⁴⁺ core. Both were obtained by zinc reduction of [Mo₃OBr₆(O₂CCH₃)₃]^– in the presence of (NBu₄) Br (2) or PMe₃ and NaBF₄ (3), and each was characterized crystallographically. Compound (2) crystallized in space group Cc with unit cell dimensionsa=25.037(5) Å,b=12.827(2) Å,c=21.484(4) Å, =122.96(1)⁰,V=5790(3) ų,Z=4. While the anion has no crystallographically required symmetry, its virtual symmetry is C_3v . The Mo-Mo distances are 2.619(2) Å, 2.610(3) Å, 2.644(2) Å, with a mean value of 2.624[14] Å. Compound (3) crystallized in space groupP2₁/c with unit cell dimensionsa=10.846(2) Å,b=25.033(5) Å,c=12.641(5) Å, =94.74(2)⁰,V=3420(2) ų,Z=4. The cation occupies a general position but has virtual C_3v symmetry, with Mo-Mo distances of 2.601(2) Å, 2.610(2) Å, 2.627(2) Å, with a mean value of 2.613[14] Å. Thus the anionic and cationic Mo₃ clusters in (2) and (3), respectively, have average Mo-Mo distances that are equal within experimental error. Compound (4), [NEt₄]₂ [W₃OCl₆(O₂CCH₃)₃] is the first 9-electron compound of this type containing tungsten. It was prepared by reduction of [Et₄N][W₃OCl₆(OAc)₃] in benzene with Na/Hg. It crystallized in space groupP2₁2₁2₁ with unit cell dimensionsa=11.076(2) Å,b=14.345(2) Å,c=21.026(3) Å,V=3574(1) ų,Z=4. The anion resides on a general position but has virtual C_3v symmetry, with W-W distances of 2.577(1) Å, 2.612(1) Å, 2.584(1) Å and a mean value of 2.591[15] Å.     

KINETICS AND MECHANISM FOR INTRAMOLECULAR ISOMERIZATION OF HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 TO Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9

Abstract

The kinetics for isomerization of HRu₃ (μ₃-η³-EtSCCMeCMe)(CO)₉ TO Ru₃(μ-SEt) (μ₃-η³-CCMeCHMe)(CO)₉, were determined. The overall process involves C[sbnd]H elimination, C[sbnd]S and Ru[sbnd]Ru bond cleavage and Ru₂(μ-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH^? = 127(3) kJ/mol, ΔS^?= 56(11) J/mol-K) and from the pressure dependence (0[sbnd]207 MPa, ΔV^? ₀ +12.7(1.1) cm³/mol, Δβ^? = +0.037(0.012) cm³/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metal-metal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C[sbnd]H elimination alone and CO dissociation is not involved.     

Os3(CO)9(μ3-AsC6H4CH3)(μ3-C6H3CH3) synthesis and crystal structure

One of the products of the reaction of the activated cluster Os₃(CO)₁₁(NCMe) with As(p-tol)₃ in refluxing nonane has been shown by spectroscopic and X-ray crystallographic methods to be Os₃(CO)₉(μ₃-AsC₆H₄CH₃)(μ₃-C₆H₃CH₃), which contains a benzyne moiety bonded asymmetrically from one carbon to one osmium via a σ bond and from a second carbon to form a bridge between the remaining two osmium atoms.     

Reaktionen von Nitrosylkomplexen: VIII. Ein alternativer Weg zu Cp3Co3(μ3-NO)2 sowie Synthese des isoelektronischen Clusters Cp3Co2Fe(μ3-NH)(μ3-NO)

Treatment of CpCo(C₂H₄)₂ with NO in hexane yields Cp₃Co₃(μ₃-NO)₂ together with the dinitrosoethane complex CpCo(NO)₂C₂H₄; the mixture of these known compounds can easily be separated. The reaction of [CpFeNO]₂ with excess CpCo(C₂H₄)₂ in THF gives Cp₃Co₂Fe(μ₃-NH)(μ₃-NO) as the main product, which is an isoelectronic congener of Cp₃Co₃(μ₃-NO)₂. Another isoelectronic species of possible composition Cp₃CoFe₂(μ₃-NH)₂ is found as a by-product.     

[{(C5Me4R)Ru}3Ru(η3-As3)(μ3,η3-As3)(μ3-As)3], arsenreiche Vierkerncluster

The interaction of [(η⁵-C₅Me₄R)Ru(CO)₂]₂ (1a: R = Me, 1b: R = Et) with yellor arsenic, As₄, affords besides the pentaarsaruthenocenes [(η⁵-As₅)Ru(η⁵-C₅Me₄R)] (2a, 2b) the tetranuclear clusters [{(η⁵-C₅Me₄R)Ru}₃Ru(η³-As₃)(μ₃,η³-As₃)(μ₃-As)₃] (3a, 3b). The structure of 2b and 3b has been elucidated by X-ray analysis.     

三核钼簇合物(Me4N)[Mo3(μ3-O)(μ-Cl)3(μ-O2CH)3Cl3]的制备和晶体结构测定

标题簇合物系通过液相氧化低价钼(MoCl3)制得,晶体属正交晶系,空间群为D2h[16]-Pmnb,晶胞参数:α=11.403(1),b=12.345(2),c=14.292(2)A,V=2011.8(8)A[3].Z=4,Dc=2.396g.cm[-3].使用四圆衍射仪收集衍射数据,晶体结构用重原子法解出,经全矩阵最小二乘修正,R=0.050,Rw=0.056.簇阴离子结构属M1型三核钼簇构型,Mo-Mo键2.577A;Mo-O-μ3键1.982A.还讨论了桥原子、键级以及配体对Mo-Mo键的影响。     

Redox behavior of trinuclear M3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(Co)9 and tetranuclear RuM3 3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(Co)12 (M=Ru or Os; and Fc=ferrocenyl) clusters. Electronic interaction between the ferrocenylacetylide ligand and the metal core of the cluster

The redox properties of the clusters Ru₃(CO)₁₂(1), Ru₃(μ-H)(μ₃-μ¹:μ²:μ²-C₂Fe)(CO)₉ (2), OS₃(μ-H)(μ₃-μ¹:μ²:μ²-C₂Fe)(CO)₉ (3), Ru₄(μ-H)(μ₄-μ¹:μ¹:μ¹:μ²-C₂Fe)(CO)₁₂ (4), and RuOS₃(μ-H)(μ₄-μ¹:μ¹:μ¹:μ²-C₂Fe)(CO)₁₂ (5) in THF have been studied by cyclic voltammetry in the temperature range from ?60 to +20°C. It was demonstrated that reversible one-electron oxidation of the ferrocenyl fragment in clusters 2–5 occurs at more positive potentials (δE ⁰=0.15–0.26 V) than that of free ferrocene. This is indicative of the electron-withdrawing character of the cluster core with respect to the ferrocenylacetylide ligand. The electron-withdrawing effect of the metal core is more pronounced in tetranuclear clusters4 and 5 than in trinuclear clusters2 and3. Unlike complexes1–3, which undergo irreversible reduction, complexes4 and5 undergo reversible one-electron reduction to form the corresponding radical anions4 ^? and5 ^?.     

CRYSTAL STRUCTURE AND REACTIVITY OF (Et_4N) [Mo_3(μ_6-O)-(μ-Cl)_3(μ-OAc)_3Cl_3]

<正> (Et4N)[Mo3(μ3-O)(μ-Cl)3(μ-OAc)3Cl3], C14H29Cl6Mo3NO7, Mr = 823.92, triclinic, P1, a = 17. 508(4), b = 19. 602(3), c=8. 091(2)A, α=91. 25(2)°, β= 96. 56(2)°,γ= 83. 61(2)°, V = 2741(1)A3, Z = 4, Dc = 2.00g/cm3, MoKa (λ=0. 71069A), μ= 19. 44cm-1, F(000) = 1616, T = 23℃, final R = 0. 055, Rw = 0. 068 for 5728 unique intensity data (I≥3σ(I)).The molecule consists of cluster aniorn [Mo3(μ3-O) (μ-Cl)3(μ-OAc)3Cl3]- and cation (Et4N) + . There are two independent molecules in an asymmetric unit whose cluster anions A and B have the same configuration except for some bonding parameters. The cluster core may be described as an equilateral {Mo3} triangle with a capping O atom and three bridging Cl atoms below and above it respectively. In addition, each pair of Mo atoms is bridged by an acetate group and each Mo atom is further coordinated to a terminal chlorine atom. The three Mo - Mo bonds are 2. 587 (2), 2.587(2), 2. 582(2) A for cluster anion A and 2. 587(2), 2.595(2), 2.577 (2) A for cluster a     

CRYSTAL STRUCTURE OF (Et_4N)2 [Mo_3 (μ_3-O) (μ_3-Cl) (μ-Cl)_3 Cl_6]·EtOH

<正> Mr=963.9, monoclinic, P21/c, a=11.379(3), b=20.766(2), c=14.487(3) A,β=91.49(2)°, V=3518.9A3, Z=4, Dm=1.81, Dx=1.819 g·cm-3, MoKα radiation, λ=0.71073A, μ=18.167, F(000)=1916, T=293 K, R=0.040 for 3261 reflections. The structure consists of two sets of tetraethylammonium cations and trinuclear Mo cluster anions. The cluster skeleton is formed by three Mo atoms arranged in an isosceles triangle with a Cl and an O atoms as capping ligands.     

[(O)MoCu_3(μ_3-S)_3(μ_3-Cl)(PPh_3)_3]·2THF的合成及其晶体结构

固体化合物(NH_4)_6Mo_7O_(24)·4H_2O和(PPh_3)_2CuCl与饱和液体NH_4HS反应获得桔红针状标题晶体。晶体空间群为P2_1/c,晶胞参数a=11.742(2),b=28.186(7),c=19.304(3),β=100.57(2)°,V=6280.4(?)~3,D_c=1.46g/cm~3,Z=4,F(000)=2816。在3≤2θ≤45°范围内收集到8414个独立衍射强度数据,其中3856个I≥1.5σ(I)强度数据参加结构计算。标题化合物分子是以{MoCu_3S_3Cl}类立方烷型簇为核心的分子,Mo—Cu的平均距离为2.716。