Low-temperature X-ray diffraction study of [CuII(1,10-C12H8N2)3]2+{CoIII[η5-(3)-1,2-C2B9H11]2} 2? ·CH3CN

Single crystal XRD is used to study the crystal structure of a new compound containing the dicarbollyl cluster anion Co(III) with the composition [CuPhen₃][Co(C₂B₉H₁₁)₂]₂·CH₃CN, where Phen is 1,10-phenanthroline. The crystallographic data: C₄₆H₇₁B₃₆N₇Co₂Cu, M = 1292.66, monoclinic system, P2₁/c space group, unit cell parameters a = 14.7178(2) ?, b = 19.5640(4) ?, c = 22.8663(5) ?, β = 106.6601(7)°, V = 6307.75(33) ?³, Z = 4, d _x = 1.361 g/cm³, T = 100 K, μ = 0.90 mm⁻¹. The structure is solved by the direct method and refined by the full-matrix LSM in an anisotropic-isotropic (for H atoms) approximation up to the final agreement factors R ₁ = 0.0370, wR ₂ = 0.0869 for 13,807 I _hkl ≥ 2 σ _I out of 18,295 measured I _hkl . The structure consists of [CuPhen₃] cations, Co(C₂B₉H₁₁)₂ anions, and acetonitrile molecules MeCN. The central Cu atom in the cation in the general position, and its coordination geometry is a distorted extended octahedron formed by six nitrogen atoms of the three bidentate Phen ligands. The coordination of Cu(II) in the cation is (2+2+2) with two long axial and four shorter equatorial Cu-N bonds, whose average lengths are 2.239(2) ? and 2.077(1) ? respectively. Each anion has its own position of the -C₂-groups; for Co(1), it is a quasi-gauche-configuration; for Co(2), a quasi-trans-configuration.     

Synthesis of (C8H11N)2·Zn(OAc)2, (C8H11N)2·Cu(OAc)2, and (C8H11N)2·CuCl2 complexes and application to the Henry reaction

(C₈H₁₁N)₂·Zn(OAc)₂ (1a), (C₈H₁₁N)₂·Cu(OAc)₂ (1b), and (C₈H₁₁N)₂·CuCl₂ complexes are synthesized by a simple one-pot method. The crystal structures of 1a, 1b, and 1c are determined by X-ray crystallography. The complexes are also characterized by NMR, IR, MS, and elemental analysis and used as the catalysts applied to the Henry reaction; moderate to high yields are obtained at room temperature.     

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [Cp*Ru(Me2S-C2B9H10)RuCp*]+

The structures of the metallacarborane cations [(-9-Me₂S-7,8-C₂B₉H₁₀)Ni(-Cp)Ni(-9-Me₂S-7,8-C₂B₉H₁₀)]⁺ (2) and [Cp*Ru(Me₂S-C₂B₉H₁₀)RuCp*]⁺ (4b) were established by X-ray diffraction analysis. These results confirmed the triple-decker structure proposed for complex 2 earlier, whereas complex 4b proved to be 13-vertex dimetallacarborane rather than the triple-decker complex, as has been suggested earlier.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1883, September, 2004.     

RE(C5H8NS2)3(C12H8N2)的标准摩尔生成焓

在无水乙醇中, 使低水合氯化稀土 (RE = Ho, Er, Tm, Yb, Lu) 与吡咯烷二硫代氨基甲酸铵 (APDC)和1,10-菲咯啉 (o–phen•H₂O) 反应, 制得其三元固态配合物. 用化学分析和元素分析确定它的组成为RE(C₅H₈NS₂)₃(C₁₂H₈N₂) (RE = Ho, Er, Tm, Yb, Lu). IR光谱说明RE³⁺ 分别与3个PDC^–的6个硫原子双齿配位, 同时与o–phen的2个氮原子双齿配位, 配位数为8. 用精密转动弹热量计测定了它们的恒容燃烧热△_cU分别为(-16788.46 ± 7.74), (-15434.53 ± 8.28), (-15287.80 ± 7.31), (-15200.50 ± 7.22)和(-15254.34 ± 6.61) kJ•mol^-1; 并计算了它们的标准摩尔燃烧焓△_cH_m^θ和标准摩尔生成焓△_fH_m^θ分别为( -16803.95 ± 7.74), (-15450.02 ± 8.28), (-15303.29 ± 9.28), (-15215.99 ± 7.22), (-15269.83 ± 6.61) kJ • mol^-1和 (-1115.42 ± 8.94), (-2477.80 ± 9.15), (-2619.95 ± 10.44), (-2670.17 ± 8.22), (-2650.06 ± 8.49) kJ•mol^-1.     

Binuclear iridium complexes containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalocogenolato ligands: Molecular structures of the complexes [(CODIr)2(μ2-S2C2(B10H10))] and [(CpIr)2(μ2-Se2C2(B10H10))]

Four binuclear iridium complexes with a chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands [Ir₂(COD)₂(μ₂-E₂C₂B₁₀H₁₀)] [E = S (3a), Se (3b)] [(Cp^∗Ir)₂(μ₂- E₂C₂B₁₀H₁₀)] [E = S (5a), Se (5b)] have been synthesized through different method. The formal oxidation state of iridium in complexes 3 and 5 are I and II, respectively, due to the different electron donor coordinated to the iridium center. All four complexes 3a-5b are characterized by IR, ¹H, ¹³C, ¹¹B NMR spectra and elemental analyses. The molecular structures of complex 3a and 5b have been determined by X-ray crystallographic analysis, only 5b shows the metal-metal interaction between the two iridium atoms.     

[Mn(NH2NHCO2C2H5)3](NO3)2的晶体结构和热分解机理

[Mn(ECZ)₃](NO₃)₂ is newly prepared by the aqueous solutions of Mn(NO₃)₂ and ethyl carbazate (ECZ). The crystal structure has been determined by X-ray crystal diffraction analysis. It belongs to monoclinic with space group of P2₁/n. The crystal parameters are: a=1.3974(2) nm, b=0.8796(2) nm, c=3.4322(7) nm, β=91.25(1) °, V= 4.2175(1) nm³, Z=8. Its molecular weight is 491.30. Mn²⁺ is located on the center of the molecular structure. Ethyl carbazate serves as a bidentate ligand which coordinates to the metal cations with its carbonyl oxygen atom and the terminal hydrazine nitrogen atom, forming five-member chelating rings, and three such rings are formed in each molecule. The coordination number of the metal ion is six and the coordination configuration of the central ion is octahedral. Specially, antimer configuration phenomenon is found in the molecule. The complex is further characterized by element analysis and IR measurements. The thermal decomposition mechanism is studied by using TG-DTG and DSC techniques. CCDC: 215675.     

(C6H8N3)+I3-和[(Cu3I4)(C8H17N2)]配体原位合成与结构表征

在溶剂热条件下, 以原位反应为基础合成了两个碘化物(C6H8N3)+I3-(1, C6H8N3=2,3-dihydroimi-dazo[1,2-a]pyrimidin-1-ium, 2,3-二氢咪唑[1,2-α]-嘧啶鎓阳离子)和[(Cu3I4)(C8H17N2)](2, C8H17N2=N-ethyl-4-aza-1-azonia-bicyclo[2.2.2]octane, N-乙基三乙烯二铵阳离子). 用元素分析、粉末X射线衍射及单晶X射线衍射等对化合物进行了表征. 结果表明, 化合物1属于三斜晶系, P1空间群, a=0.74281(15) nm, b=0.84241(17) nm, c=0.9993(2) nm, α=82.02(3)°, β=83.30(3)°, γ=82.92(3)°, V=0.6114(2) nm3. 化合物2属于单斜晶系, P21/c空间群, a=0.68924(14) nm, b=1.0786(2) nm, c=2.2779(5) nm, β=94.84(3)°, V=1.6874(6) nm3. 在两个化合物合成中存在两种不同类型的配体原位合成反应, 即化合物1的2-氨基嘧啶和乙醇的成环反应与化合物2的三乙烯二胺和乙醇的烷基化反应.     

1,2,3,4,7-Pentamethylindenyl complex [(η5-C9H2Me5)RhI2]2 as a synthon for the [(η5-C9H2Me5)Rh]2+ fragment

The reaction of the iodide complex [(η⁵-C₉H₂Me₅)RhI₂]₂ (1) or the acetonitrile complex [(η⁵-C₉H₂Me₅)Rh(MeCN)₃]²⁺ with Tl[Tl(η-7,8-C₂B₉H₁₁)] afforded rhodacarborane (η⁵-C₉H₂Me₅)Rh(7,8-C₂B₉H₁₁) (2). The cationic triple-decker complex with the bridging boratabenzene ligand [Cp*Fe(μ-η:η-C₅H₃Me₂BMe)Rh(η⁵-C₉H₂Me₅)]²⁺ (3) was synthesized by the reaction of the nitromethane solvate [(η⁵-C₉H₂Me₅)Rh(MeNO₂)₃]²⁺ with the sandwich compound Cp*Fe(η-C₅H₃Me₂BMe). The structure of 2 was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1623–1625, August, 2008.     

具有[344484]笼状结构单元的微孔磷酸镓Ga3P2O8(OH)3(H2O)的合成、晶体结构及表征

Open-framework metal phosphates have been the subject of intense research owing to their interesting structural chemistry and potential applications in catalysis and ion exchange. The gallium phosphate family has exhibits rich structural chemistry. A novel gallium phosphate Ga₃P₂O₈(OH)₃(H₂O)(GaPO-CJ36) has been prepared in a hydrothermal reaction system of GaO(OH)-H₃PO₄-Co(chxn)₃Cl₃-H₂O at 180 ℃ for 7 days. Single-crystal X-ray analysis shows that GaPO-CJ36 crystallizes in the P2₁/c space group with a=1.833 35(12) nm, b=0.503 94(3) nm, c=1.062 90(9) nm, V=0.982 01(12) nm³, and Z=4. The connection of GaO₂(OH)₃(H₂O) octahedra, PO₄ and GaO₄ tetrahedra through vertex oxygen atoms forms a three-dimensional open framework, which contains 8-ring channels along the [010] direction. Its structure is composed of interesting [3⁴4⁴8⁴] cages, which have not been found in known gallium phosphates. CSD: 416779.     

Unusual ion UO4? formed upon collision induced dissociation of [UO2(NO3)3]?, [UO2(ClO4)3]?, [UO2(CH3COO)3]? ions

The following ions [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ were generated from respective salts (UO₂(NO₃)₂, UO₂(ClO₄)₃, UO₂(CH3COO)2) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO₄ ⁻ ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U^VI compound, in which oxygen atoms bear unpaired electron and negative charge.     

Complexation between N-allylmorpholinium derivatives and copper(I) halides. Synthesis and crystal structure of π-complex {[C4H8ONH(C3H5)]+}2[Cu2Cl4]2?

Copper(I) -complex {[C₄H₈ONH(C₃H₅)]⁺}₂[Cu₂Cl₄]^2– (I) was obtained by ac electrochemical synthesis from N-allylmorpholine hydrochloride and copper(II) chloride in ethanol and structurally characterized. In structure I, copper and chlorine atoms form unique noncentrosymmetric Cu₂Cl ₄ ^2– fragments. Both crystallographically independent N-allylmorpholinium cations are involved in the -interaction and are coordinated by the copper atom through the C=C bond of the allyl group. The trigonal pyramidal environment of the Cu(1) atom is composed of three chlorine atoms and the C=C bond, while the Cu(2) atom coordinates two chlorine atoms and the C=C bond forming a planar triangle. The extremely strong N-CCl hydrogen bond (HCl 2.2 ) prevents the Cl(1) atom from acting as a bridge and favors the formation of fragments Cu₂Cl ₄ ^2– .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 306–310.Original Russian Text Copyright © 2005 by Goreshnik, Davydov, Myskiv.     

Synthesis of the cyclooctadiene and cyclooctenediyl cobalt complexes. Structures of [(η2,η2-cyclooctadiene)Co(η-1,2,4,5-C6H2Me4)]BF4 and [(η1,η3-cyclooctenediyl)Co(η-9-SMe2-7,8-C2B9H10)

Cobaltacarboranes (η¹, η³-cyclooctenediyl)Co(Carb) (Carb = η-9-SMe₂-7,8-C₂B₉H₁₀, η-1-tBuHN-1,7,9-C₃B₈H₁₀) were synthesized by the reaction of the carborane anions [Carb]⁻ with the acetonitrile complex [(η¹, η³-cyclooctenediyl)Co(MeCN)₃]⁺ generated in situ upon the dissolution of [(η¹, η³-cyclooctenediyl)Co(η-1,4-C₆H₄Me₂)]⁺ in MeCN. The structures of (η¹,η³-cyclooctenediyl)Co(η-9-SMe₂-7,8-C₂B₉H₁₀ and [(η²,η²-cyclooctadiene)Co((η-1,2,4,5-C₆H₂Me₄)]BF₄ were determined by X-ray diffraction analysis.     

Nonsymmetrical iron bis(carborane) complexes (η-1-ButNH-1,7,9-C3B8H10)Fe(η-9-L-7,8-C2B9H10) (L = SMe2, NMe3)

Visible light irradiation of the benzene complex [(η-1-Bu^tNH-1,7,9-C₃B₈H₁₀)Fe(η-C₆H₆)]⁺ in the presence of the charge-compensated carborane anions [9-L-7,8-C₂B₉H₁₀]⁻ (L = SMe₂, NMe₃) affords ferracarboranes (η-1-Bu^tNH-1,7,9-C₃B₈H₁₀)Fe(η-9-L-7,8-C₂B₉H₁₀). Their structures were established by X-ray diffraction analysis.     

The preparation and crystal structure of (η-C5H5)(OC)3Mo(CH2)3C6H5

The reaction of with p-CH₃C₆H₄S(O)₂O(CH₂)₃C₆H₅ produces (η⁵-C₅H₅)(OC)₃Mo(CH₂)₃C₆H₅. This is only the second structurally characterized organometallic species in which an aromatic moiety is separated by three or more methylene groups. The alkyl chain adopts a staggered conformation, the Mo-C(1)-C(2)-C(3)-C(4) unit is nearly coplanar, and the alkyl chain eclipses the trans-carbonyl group on Mo. NMR evidence indicates that this conformation is preserved in solution.     

Stable radical adducts of diisopropylphosphoryl radicals with fullerene complexes (η2-C60)Os(CO)(PPh3)2(CNBut) and (η2-C70)Os(CO)(PPh3)2(CNBut)

It was determined by ESR spectroscopy that the UV irradiation of toluene solutions containing Hg[P(O)(OPrⁱ)₂ and the complex (²-C₆₀)Os(CO)(PPh₃)₂(CNBu^t) produces six stable regioisomeric adducts of phosphoryl radicals with complexes, which are not demetallated under UV irradiation and do not dimerize in the absence of UV irradiation. This is caused by the addition of the phosphoryl radicals to the carbon atoms of fullerene localized near the metal-containing moiety. The addition of the phosphoryl radicals to (²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) gives rise to the formation of nine stable regioisomeric radical adducts. A comparison of the composition of regioisomers of the radical adducts of C₇₀ with the phosphoryl radicals, which were formed directly from C₇₀ and from the radical adducts of ²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) by the demetallation of the latter, revealed an orienting effect of the osmium-containing moiety on the addition of the phosphoryl radicals to the fullerene complex.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1968–1972, September, 2004.     

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。     

X-ray and conformation analysis of the new trinuclear cluster of osmium Os3(μ,η2-OCC6H5)(η3-C3H5)(CO)9

The crystal structure of the Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ cluster synthesized by the reaction of the (μ-H)Os₃(μ-O=CC₆H₅)(CO)₁₀ complex with allylamine in chloroform was determined by X-ray analysis. Prolonged storage of the reaction mixture led to N-C bond cleavage in allylamine and η³-addition of the allyl fragment at one of the Os atoms (Os-C 2.246 ?, 2.248 ?, and 2.273 ?). The unit cell parameters of the complex are a = 9.494(1) ?, b = 10.479(1) ?, c = 12.474(2) ?, α = 84.55(1)°, β = 70.08(1)°, γ = 70.72(1)°, V = 1255.8(4), ?³, space group P , Z = 2; C₁₉H₁₀O₁₀Os₃; d _calc = 2.922 g/cm³, 3085 I _hkl > 2σ _I of 3611 collected reflections; R = 0.0252. The structure of Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ is molecular. The plane of the Os₃ triangle and the OsCOOs plane are connected according to the “butterfly” principle with an angle of 103.4° between them. The Os-Os distances in the cluster core vary from 2.836(1) ? to 2.844(1) ?; the Os-C_carb distances are 1.88(1)–1.97(1) ?; the distances to the atoms of the bridging ligands are Os-C 2.11(1) ?, Os-O 2.14(1) ?; the O-C bridging bond is 1.24(1) ?. of the Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ triosmium cluster were studied theoretically. The potential curve of the internal rotation of the allyl ligand relative to the Os(1)-C(9) bond was determined. The rotation barrier of the allyl ligand in crystal relative to the Os(1)-C(9) bond is 8.38 kJ/mol, and the rotation of the ligand is not hindered. The effects of the intra-and intermolecular interactions on the conformation state of the cluster complex are considered. Original Russian Text Copyright ? 2008 by V. A. Maksakov, N. V. Pervukhina, N. V. Podberezskaya, M. Yu. Afonin, V. A. Potemkin, and V. P. Kirin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 5, pp. 926–932, September–October, 2008.     

两个闭式十一顶钌硼烷簇合物[(PPh3)(p-BrC6H4CO2)2RuB10H8]和[(PPh3)2Ru(p-BrC6H4CO2)(PPh3)RuB10H9]的合成与晶体结构

[RuCl₂(PPh₃)₃],B₁₀H₁₀^2-与p-BrC₆H₄COOH在CH₂Cl₂中回流, 得到两个闭式十一顶钌十硼烷簇合物: [(PPh₃)(p-BrC₆H₄CO₂)₂RuB₁₀H₈] (1) 和 [(PPh₃)₂Ru(PPh₃)(p-BrC₆H₄CO₂)RuB₁₀H₉] (2), 并进行了元素分析、红外光谱、¹H核磁共振谱、¹³C核磁共振谱、X-射线单晶衍射表征. 簇合物1属于单斜晶系，空间群为C2/c, a = 2.569(4) nm, b=1.546(2) nm, c=1.927(3) nm, β=95.11(2)°, Z=8, V=7.622(21) nm³, D_c=1.533 Mg/m³, F(000)=3472, S=1.009, R=0.0418, wR=0.0775; 簇合物2属于三斜晶系, 空间群为P-1, a = 1.3142(3) nm, b=1.3761(3) nm, c=1.8503(4) nm, α=90.445(4)°, β=105.950(4)°, g=108.980(4)°, Z=2, V=3.0251(12) nm³, D_c=1.434Mg/m³, F(000)=1316, S=1.007, R=0.0464, wR=0.1175. 单晶结构分析表明, 两个簇合物的中心都具有一个闭式1:2:4:2:2堆砌结构的十一顶{RuB₁₀}金属硼烷骨架, 硼笼开口处具有船式构象的环状的六个硼原子对Ru(1)原子呈h⁶船式配位. 在簇合物1中, 钌原子有三个簇外配体, 一个三苯基膦, 两个对溴苯甲酸根. 对溴苯甲酸根上另外的两个氧原子分别取代了B(2)和B(3)上的氢原子, 从而在簇合物的两侧形成两个对称的Ru-O-C-O-B五员环. 簇合物2是一个双金属钌硼烷簇合物, Ru(2)通过一个Ru-Ru键和两个{RuH_mB}桥键与簇合物中心{RuB₁₀}相连, 从而在簇外形成了一个变形的Ru(1)-Ru(2)-B(3)-B(6)四面体结构.     

Mixed-Valence 24-Vanadophosphate Decorated with Six RuII(dmso)3 Groups: [{RuII3(dmso)9PVV11VIVRuIIIO37(OH)3}2]8?

The mixed-valence 24-vanadophosphate (1) has been synthesized and characterized in the solid state by IR, magnetism, EPR, XPS, and elemental analysis. Single-crystal X-ray analysis was carried out on (Na-1), which crystallizes in the triclinic system, space group , with a = 17.168(3) ?, b = 18.1971(14) ?, c = 20.1422(13) ?, α = 114.753(3)°, β = 99.390(4)°, γ = 95.124(4)°, and Z = 2. Polyanion 1 has an unusual, open structure composed of 2 Ru^IIIO₆ octahedra, 2 V^IVO₆ octahedra, 14 V^VO₅ square-pyramids, 8 V^VO₄ tetrahedra, and 2 PO₄ tetrahedra which are all directly linked via edges and corners. The outer surface of 1 is decorated with six Ru^II(dmso)₃ groups. XPS studies on Na-1 confirm the presence of 2 Ru^III and 6 Ru^II as well as 22 V^V and 2 V^IV centers. Magnetic susceptibility data on Na-1 show that the V^IV–Ru^III pairs are coupled antiferromagnetically, with J ₁ = −13 K and J ₂ ∼ −3 K. We did not detect any peak in our EPR measurements on Na-1, thus supporting the conclusion that Na-1 is diamagnetic in its ground state. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. In Memoriam Prof. F. A. Cotton