The Synthesis of the Arene Clusters Ru6C(CO)14(η6-Arene) (Arene = C6H5CHMe2, C6H5C4H9, C6H5C3H7, and C6H5C3H5)

On reaction with Ru₃(CO)₁₂, isopropenylbenzene and 4-phenyl-l-butene undergo hydrogenation, to yield the clusters, Ru₆C(CO)₁₄(⁶-C₆H₅CHMe₂) 1 and Ru₆C(CO)₁₄(⁶-C₆H₅C₄H₉) 2, respectively. With allylbenzene, both hydrogenation and isomerization occurs affording Ru₆C(CO)₁₄(⁶-C₆H₅C₃H₇) 3 and Ru₆C(CO)14(⁶-C₆H₅C₃H₅) 4. The structures of 1 and 2 have been established by single crystal X-ray diffraction. One of the Ru–Ru bond lengths in 2 is unusually long and extended Hückel molecular orbital calculations have been used in an attempt to rationalize this feature.     

C3N6H6(H3BO3)2的合成及晶体结构

以三聚氰胺和硼酸为原料在水溶液中反应合成出了一种新的BCN化合物先驱体C3N6H6(H3BO3)2。XRD表征结果表明三聚氰胺和硼酸的最佳配比为1∶3(物质的量比)。用单晶X-射线衍射分析法测定了该化合物的晶体结构。该化合物属单斜晶系,空间群为P21/C,晶胞参数为a=0.3597(7)nm,b=2.0105(4)nm,c=1.4112(3)nm,α=90,°β=92.07(3),°γ=90,°V=1.0199(3)nm3,Z=4,D c=1.627g.cm-3,μ(MoKα)=0.144mm-1,F(000)=520。晶体结构经全矩阵最小二乘法修正,最终可靠因子R1=0.0519,wR2=0.1361。该化合物是由C3N6H6分子和H3BO3分子通过氢键加合组装形成的三维超分子结构化合物。     

Reactions of ytterbium(II) bis(indenyl) complex (C9H7)2Yb(thf)2 with 2,2’-bipyridine and 1,4-bis(2,6-diisopropylphenyl)-1,4-diazabuta-1,3-diene. Structures and properties of (C9H7)2Yb(bipy) and (C9H7)2Yb(2,6-Pri 2C6H3NCHCHNC6H3Pri 2-2,6) complexes

The reaction of the ytterbium(II) bis(indenyl) complex (C₉H₇)₂Yb(thf)₂ (1) with 2,2’-bipyridine afforded the diamagnetic (C₉H₇)₂Yb(bipy) compound (2), whose structure was established by X-ray diffraction analysis. Under similar conditions, the reaction of complex 1 with 1,4-bis(2,6-diisopropylphenyl)-1,4-diazabuta-1,3-diene (DAD) led to oxidation of ytterbium giving rise to the paramagnetic (C₉H₇)₂Yb(DAD) complex (3). Magnetic measurements, X-ray diffraction study, and ¹H NMR spectroscopy in benzene confirmed the trivalent state of the ytterbium atom and the radical-anionic nature of the diazadiene ligand in complex 3. In the complex 3—solvent system, the oxidation state of metal depends on the coordination ability of the solvent. In benzene, complex 3 exists as (C₉H₇)₂Yb^III(DAD^·-), whereas (C₉H₇)₂Yb^II(thf)₂ and DAD⁰ are present in THF.     

Cyclohexylamine) 2 M(CN) 4 ⋅2C 6 H 6 (M = Cd or Hg)

Two new title compounds have been prepared in powder form. Their spectral data are found to be consistent with the structure foundin Hofmann-T_d-type clathrates.     

Synthesis and structures of the six-coordinate donor-acceptor complexes R3(C6H4O2)Sb…L (R=Ph, L=OSMe2 or ONC5H5; R=Me, L=ONC5H5 or NC5H5) and R3(C2H4O2)Sb…L (R=Ph, L=ONC5H5; R=Cl or C6F5, L=OPPh3)

One-pot oxidation of R₃Sb (R=Ph, Me, Cl, or C₆F₅) withtert-butyl hydroperoxide in the presence of 1,2-diols and monodentate donor compounds was studied. The structures of the resulting neutral organic donor-acceptor Sb^V complexes, Ph₃(C₆H₄O₂)Sb…OSMe₂, Ph₃(C₆H₄O₂)Sb…ONC₅H₅, Me₃(C₆H₄O₂)Sb…ONC₅H₅, Me₃(C₆H₄O₂)Sb…NC₅H₅, Ph₃(C₂H₄O₂)Sb…ONC₅H₅, and Cl(C₆F₅)₂(C₂H₄O₂)Sb…OPPh₃, were established by X-ray diffraction analysis. In these complexes, the coordination environment about the Sb atoms is a distorted octahedron. The Sb?O(N) distances and the Sb?O?E angles (E=S, N, or P) vary over wide ranges.     

[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O的 合成、晶体结构及磁性质

Mn(O2CMe)2·4H2O、咪唑、苯甲酸和N(n-Bu)4MnO4在无水乙醇溶剂中反应,制备得到锰的三核μ3-O桥联配位化合物[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O.该配位化合物的X射线单晶衍射表明,其属于单斜晶系,空间群P21/C,晶胞参数：a=1.52832(19)nm,b=1.9722(2)nm,c=2.1023(3)nm,β=92.597(3)°,Z=4.变温磁化率(5～280K)研究表明,该配位化合物中3个锰离子在低温下存在弱的反铁磁性耦合,交换积分J=-2.34cm^-1。     

Crystal structure of Μ2, η2, Σ2-nitrato-η2, Σ2-nitrato-bis(1-ethyltetrazole-N4)copper(II) Cu(C3H6N4)2(NO3)2 = [Cu(C3H6N4)2(NO3)(NO3)2/2]∞

The complex compound of copper(II) nitrate with 1ethyltetrazole (ettz), Cu( C₃H₆N₄)₂(NO₃)(NO₃)_2/2] is studied by Xray diffraction analysis (“Syntex P2₁” automatic diffractometer, CuK_a radiation, graphite monochromator, 6/26 scan mode with V_min = 3.91 deg/min, the total number of data collected 3544 l_hkb including 3141 nonextinct l_hkl > 0, a correction for absorption (Μ = 25.08 cm^-1) applied by integrating over the crystal faces). The parameters of the orthorhombic unit cell (space group Pccn) are a = 15.436(3), b = 20.198(5), c = 19.587(3) Å, V_cell = 6107(2) Å^{3, Z} = 16, d_calc = 1.670 g/cm³. The two crystallographically independent copper atoms have a distorted octahedral environment (coordination node is CuN₂O₄), coordination number (CN) is 6 = 4 + t2. In the equatorial plane, two nitrogen atoms of ettz and two oxygen atoms of NO ₃ ^? groups are trans to each other; Cu-N = 1.983(8), C-O_{NO 3} ^? = 1.978(7) Å (average). The nitrato groups fulfill chelate and bridging functions, complementing the coordination polyhedra of the copper atoms to distorted octahedra, where Cu-O_{NO 3} ^? = 2.517(7) Å (average). The compound has a chain structure; the chains stretching along [001] are packed pairwise according to the hexagonal law.     

Layered Lanthanum Complex with 3-Nitrophthalic Acid Assembled via Hydrogen Bonds-Synthesis, Structure and Characterization of [LaL(HL)(H2O)3]2·2H2O (H2L = 3-NO2C6H3(CO2H)2)

A new dinuclear centrosymmetric complex [LaL(HL)(H2O)3]2(2H2O (H2L = 3-nitrophthalic acid, NPA) was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The complex crystallizes in triclinic system, space group P-1 with a = 8.1549(16), b = 8.8856(18), c = 15.277(3)(A),α= 100.93(3),α= 90.81(3), γ= 104.56(3)°, V = 1049.8(4)(A)3, Z = 1,μ= 2.125 mm-1, Dc＝1.994 g/cm3, R = 0.0259 and wR = 0.0679. Two 3-nitrophthalates(2-) coordinate with the La3 ions in a bridging mode, and two monohydrogen- 3-nitrophthates(1-) and three waters in terminal ways, respectively. Each La3 ion is nine-coordinated to exhibit a distorted tricapped trigonal prism coordination polyhedron. Both the coordinated and crystal waters are involved in the inter- and intramolecular hydrogen bonds. The dinuclear units are linked into a 2D network structure in the ab plane via intermolecular hydrogen bonds along the axes a and b. Two crystal waters fill each rhombic pore of the network. The networks are further packed along the c axis forming a layered supramolecular structure through the C-H…O weak forces between the adjacent sheets. TGA analysis shows the complex undergoes the loss of waters of crystallization and coordination and the decomposition of ligands sequentially.     

Reactions of trans-[Pt(H2){P(C6H11)3}2] with heterocumulenes. The crystal and molecular structure of trans-[Pt{P(C6H11)3}2(H){OCHC(C6H5)2}]

Trans-PtH₂(PCy₃)₂ (1) reacts with phenylisocyanate (2) and with diphenylketene (3) to yield the formamido complex (4) and the vinyloxo complex (5), respectively. The structure of 5 has been determined by X-ray diffraction.     

Synthesis and Structure of Tetraphenylantimony Oximates Ph4SbON=CRR′ (CRR′ = C6H9−C6H9-2 and R = Ph,R′ = C(O)Ph)

The reaction of pentaphenylantimony and the oxime HON=CRR taken in 1 : 1 molar ratio in toluene gave tetraphenylantimony oximates Ph₄SbON=CRR (CRR = C₆H₉–C₆H₉-2 (I) and R = Ph, R = C(O)Ph (II)). According to X-ray diffraction data, the Sb atoms in I and II have a distorted trigonal-bipyramidal coordination with oximate ligands in the axial positions. The C_axSbO angles are 177.6(1)° in I and 176.58(6)° in II. The Sb–C bond lengths lie in the ranges of 2.120(4)–2.203(4) Å for I and 2.122(2)–2.181(2) Å for II. The Sb–O bond lengths are 2.120(2) Å (I) and 2.166(1) Å (II). The lengths of the intramolecular Sb···N contacts are 2.806(3) and 2.918(2) Å in I and II, respectively.     

[(C6H5 NO2)Pr(H2O)4](CrMo6O24H6)·(C6H5NO2)·2.5H2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[(C6H5NO2)2Pr(H2O)4](CrMo6O24H6)·2.5H2O,通过红外光谱和X射线单晶衍射对其进行了表征.结果表明,该化合物属于单斜晶系,C2/c空间群.a=2.3442(9)nm,b=1.3291(5)nm,c=2.458(1)nm,β=103.08(1)°,V=7.460(5)nm3,R1=0.0727,wR2=0.1903.结构分析表明,[CrMo6O24H6]3-阴离子通过端氧担载一个配位的Pr3+离子形成中性的(C6H5NO2)Pr(H2O)4(CrMo6O24H6)基团,相邻的中性基团在Ot—Pr—Ot桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构.     

Rb[C6H3(COOH)2(COO–)] · [C6H3(COOH)3] · 2H2O: Synthesis,Crystal Structure,and Properties

The salt Rb[C₆H₃(COO)₂(^–)] · [C₆H₃(COOH)₃] · 2H₂O (I) of trimesic acid was synthesized and its thermal stability and conductivity (10^–11 ohm^–1 cm^–1 at 298 K) were measured. Molecular and crystal structures of I were established by X-ray diffraction analysis. Hydrogen bonding system in complex I was detected by IR and Raman spectroscopies. X-ray diffraction data agree with vibration spectroscopy data.     

Luminescence properties of complexes Ln(Phen)(C6F5COO)3 (Ln = Tb, Eu) and Ln(C6F5COO)3 · nH2O (Ln = Tb, n = 2; Ln = Eu, n = 1). Structures of the [Tb2(H2O)8(C6F5COO)6] complex and its isomer in the supramolecular compound [Tb2(H2O)8(C6F5COO)6] · 2C6F5COOH

Complexes Ln(Phen)(C₆F₅COO)₃ (Ln = Tb, Eu; Phen = 1,10-phenanthroline) (I, II) are synthesized. At 300 K these complexes and compounds Ln(C₆F₅COO)₃ · nH₂O (Ln = Tb, n = 2; Ln = Eu, n = 1) (III, VI) possess photoluminescence (bright in the case of I and II). In the spectrum of compound I the line at 545 nm (transition ⁵ D ₄ → ⁷ F ₅) is most intense, whereas in the spectrum of compound II the most intense is the line at 613 nm (transition ⁵ D ₀ → ⁷ F ₂). The replacement of Phen by water decreases the luminescence intensity. The compound [Tb₂(H₂O)₈(C₆F₅COO)₆] · 2C₆F₅COOH (IV) is synthesized. According to the X-ray diffraction data, in structure IV the molecules of the binuclear Tb(III) complex with the C₆F₅COOH molecules form a supramolecular ensemble due to hydrogen bonding. The C₆F₅COO^? ligands perform the monodentate and bidentate bridging function, resulting in the opening of the eight-membered cycle Tb₂C₂O₄. The TbO₈ polyhedron is a distored tetragonal antiprism. The crystals of the binuclear complex [Tb₂(H₂O)₈(C₆F₅COO)₆] (V) are obtained in which the C₆F₅COO^? ligands are monodentate and tridentate bridging cyclic, which results in the closure of two four-membered cycles TbO₂C and one four-membered cycle Tb₂O₂. The TbO₉ polyhedron is a distorted monocapped tetragonal antiprism.     

Synthese und spektroskopische charakterisierung von cyclopentadienyleisen-komplexen mit PN-liganden des typs (C6H5)3−nP(NR2)n (n = 0−3; R = CH3, C2H5

The complex cations [C₅H₅Fe(CO)₂L]BF₄ (L = (C₆H₅)_3−nP(NR₂)_n; n = 0−3 R = CH₃, C₂H₅) have been obtained from the reaction of [C₅H₅Fe(CO)₂THF]BF₄ (I) with L. The reaction of I with E(NR₂)₃ (E = As, Sb; R= CH₃) is also described. Spectroscopic investigations (IR, ¹H, ¹³C and ³¹P NMR) indicate an increase in electron density on the iron center through increase of the number of P-bound NR₂ groups.     

Crystal Structure of CH(3,5-Me2-4-EtPz)2W(CO)3SnPh3·0.25C6H6 (Pz = Pyrazol-1-yl)

The reaction of triphenylstannyl-bis(3,5-dimethyl-4-ethylpyrazol-1-yl)methane with W(CO)5THF yields the title compound (C37.5H39.5N4O3SnW, Mr = 896.79) which is of triclinic,space group P1 with a = 9.755(3), b = 13.696(4), c = 14.359(5) A, α = 96.202(7), β= 93.313(6), γ=94.845(6)°, V = 1896(1) A3, Z = 2, Dc = 1.571 g/cm3, λ(MoKα) = 0.71073 A, μ= 3.728 mm-1,F(000) = 881, R = 0.0491 and wR = 0.0856 for 4242 observed reflections (I≥2σ(I)). The crystalstructural analysis indicates that bis(3,5-dimethyl-4-ethylpyrazol-1-yl)methide acts as a tridentate monoanionic K3-[N,C,N] chelating ligand, and four-membered metallacycles are found in this heterodinuclear complex.     

Tetranuclear bismuth complexes Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H6 and Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H4Me2-1,4: Synthesis and structures

X-ray diffraction study of tetranuclear organobismuth complexes Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2⁶-C₆H₆ and Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2(C₆H₄Me₂-1,4) revealed four Bi atoms connected through the bridging carboxylate ligands and the O atoms. The coordination sphere of the terminal Bi atoms includes the chelate carboxylate ligand and the 6-arene molecule. The bridging O atoms are tricoordinated, the distances between the terminal Bi atom and the center of benzene molecule (1,4-dimethylbenzene) are 3.024 Å(3.131 Å).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 4–11.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Sharutina, Ivanenko, Adonin, Starichenko, Pushilin, Gerasimenko.     

Syntheses and Crystal Structures of Sm(OAr)2(THF)3·THF and Sm(OAr)2(DME)2 (Ar = C6H2-tert-Bu3-2,4,6)

Reaction of SmI2(THF)x with 2 equivalents of NaOAr (Ar = C6H2-tert-Bu3-2,4,6)1,2-dimethoxyethane (DME) leads to the ligand-exchange reaction, and a DME-solvated complex of Sm(Oar)2(DME)2 2 was obtained. Complex 1 crystallizes in monoclinic, space group P21/c with a =10.366(5), b = 33.024(15), c = 16.123(7) (A), β= 93.197(8)°, V= 5511(4) A3, Z= 4, C52H9oO6Sm, Mr = 961.59, Dc = 1.159 g/cm3, F(000) = 2048,μ(MoKα) = 1.107 mm-1, R = 0.0844 and wR = 0.1401for 4694 observed reflections. Complex 2 crystallizes in monoclinic, space group C2/c with a =27.222(5), b = 10.6140(19), c = 17.398(4) (A), β = 110.245(3)°, V = 4716.4(16) (A)3, Z = 4,C44H78O6Sm, Mr = 853.41, Dc = 1.202 g/cm3, F(000) = 1808,μ(MoKα) = 1.285 mm-1, R = 0.0361and wR = 0.0830 for 5210 observed reflections.     

(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。     

Tris(2,4,6-trimethylphenyl)antimony dihydroxide; synthesis and reaction with sulfonic acids RSO3H (R = C6H5, CF3). Crystal structure of [2,4,6-(CH3)3C6H2]3SbO · HO3SC6H5

Tris(2,4,6-trimethylphenyl)antimony dihydroxide, Mes₃Sb(OH)₂, which was prepared by oxidation of Mes₃Sb with H₂O₂, has been shown to react with RSO₃H (R = C₆H₅, CF₃) to give the adducts Mes₃SbO · HO₃SR, the first examples of solid hydrogen-bonded adducts of a triorganoantimony oxide and an acid. The crystal structure of Mes₃SbO·HO₃SC₆H₅ has been determined. The three C(mesityl) atoms and the O atom form a distorted tetrahedron around Sb, the distortion by the bulky mesithyl groups being reflected in the CSbC angles (mean: 114.7(3)°) and the CSbO angles: (mean: 103.5(2)°). C₆H₅SO₃H is linked via a short hydrogen bond to O on Sb, with O(1) z^.;O(2) = 256(1) pm. The bond length SbO(1) 189.4(5) pm represents the shortest SbO distance ever reported.     

The Structure of Pd2(CH≡CC6H5)2(C5H7O2)3(BF3)2BF4

IR and NMR data showed that the ionic complex Pd₂(CHCC₆H₅)₂(C₅H₇O₂)₃(BF₃)₂BF₄ isolated in the reaction Pd(Acac)₂ + PA + 5BF₃OEt₂ (Acac is C₅H₇O₂, PA is phenylacetylene) is an adduct of two complexes, namely, (Acac)PdBF₄ and [(PA)₂Pd(C³-Acac · BF₃)]⁺(Acac · BF₃)^– (coordinatively unsaturated). On dissolution in deuteroacetone or deuteromethanol, the [(Acac)PdF₂BF₂Pd(C³-Acac · BF₃)(PA)₂]⁺(Acac · BF₃)^– adduct decomposed to Pd(Acac)₂, 2BF₃ · L (L = (CD₃)₂CO, CD₃OD) and the [L(PA)₂Pd(C³-Acac]⁺BF₄ ^– complex.