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.     

Synthesis,structure characterization and thermal properties of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2Bu)9(μ2-OH)3]2

Oxo/hydoxo zirconium(IV) complex of the general formula [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ has been isolated, when Zr(OⁱPr)₄ reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P6₃/m (no. 176)). Structure consists of dimers composed of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉] sub-units, linked by six μ₂-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ₂-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ proceeds with complete conversion to ZrO₂ (monoclinic form) between 603 and 803 K.     

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.     

Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

Reactions of [(dtc)₂Mo₂(S)₂(μ-S)₂] with one or two equivalents of CuBr in CH₂Cl₂ afforded two new heterobimetallic sulfide clusters, [(dtc)₂Mo₂(μ₃-S)(μ-S)₃(CuBr)] (1) and [(dtc)₂Mo₂(μ₃-S)₄(CuBr)₂] (2). Both compounds were characterized by elemental analysis, IR, UV-vis and X-ray analysis. Compound 1 contains a butterfly-shaped Mo₂S₄Cu core in which one CuBr unit is coordinated by one bridging S and two terminal S atoms of the [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety. In the structure of 2, one [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety and two CuBr units are held together by six Cu-μ₃-S bonds, forming a cubane-like Mo₂S₄Cu₂ core.     

Metallotricycle of Lanthanide Supported by a Bridging Diamide: Syntheses and Molecular Structures of {Li(THF)3[LnCl(μ2-trans-1,2-(NSiMe3)2C6H10)(μ2-Cl)]}2•2THF (Ln＝Yb, Nd)

The reactions of dilithium salt of trans-1,2-bis（trimethylsilylamino）cyclohexane with anhydrous lanthanide trichlorides LnCl3 （Ln = Yb, Nd） in THF afforded the dianionic binuclear tricycles of lanthanide chlorides {Li（THF）3[LnCl（μ2-trans-1,2-（NSiMe3）2C6H10）（μ2-Cl）]}2·2THF （Ln=Yb 1, Nd 2） in moderate yields. Both of the bridged complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that the two complexes are the analogues which have a tricyclic framework built by two bridged lanthanide metals, four nitrogens and four carbons from two diamide ligands. Each lanthanide metal coordinates to three nitrogen atoms and two chlorines to form a distorted trigonal bipyramid and connects with a lithium by a bridging chlorine.     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

Synthesis of Mo(CO)2(η-PPh2(o-C6H4)C(O)H)2 and its reaction with C60

Reaction of Mo(CO)₃(NCMe)₃ and PPh₂(o-C₆H₄)C(O)H (abbreviated as PCHO) at room temperature affords Mo(CO)₂(η³-PCHO)₂ (1), while compound 1 and the phosphine-imine complex Mo(CO)₄(η²-PPh₂(o-C₆H₄)CHNMe) (2) are obtained by using Mo(CO)₃(η³-(MeNCH₂)₃) as the reactant. Thermal reaction of 1 with C₆₀ products Mo(CO)₂(η⁴-(PPh₂(o-C₆H₄)CH)₂)(η²-C₆₀) (3) in low yield, apparently through coupling of the formyl moieties. The structures of 1 and 3 have been determined by an X-ray diffraction study. The two aldehyde groups of 1 and C₆₀ ligand of 3 are coordinated to the molybdenum atom in a π-fashion.     

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.     

Crystal structure and spectral characteristics of {[(C6H5)NH]2C=NH(C6H5)}[B(C6H5)4]·C2H5OH

A novel compound of {[(C₆H₅)NH]₂C=NH(C₆H₅)}[B(C₆H₅)₄]·C₂H₅OH is prepared and examined by single crystal X-ray diffraction. Crystal data: C₄₅H₄₄BN₃O, M = 653.64, monoclinic, space group P2₁/c, unit cell parameters: a = 24.375(2) Å, b = 17.5829(15) Å, c = 18.090(1) Å, β = 105.277(2)°, V = 7479.0(11) ų, Z = 8, d _calc = 1.161 g/cm³, T = 293 K, R ₁ = 0.064. The structure contains two crystallographically independent cations, two anions, and two solvate ethanol molecules. Three types of interactions occur between them: interionic N-H(N)⋯π and N(H)⋯π⋯H(C), π-delocalized system of Ph rings of the anions, and interaction of ions with ethanol molecules N-H⋯O-H(O)⋯π. The compound is characterized by IR and luminescence spectra. At room temperature, the emission intensity grows with time of exposure to UV irradiation. Original Russian Text Copyright ? 2008 by T. M. Polyanskaya, E. A. Il’inchik, V. V. Volkov, M. K. Drozdova, O. P. Yur’eva, and G. V. Romanenko __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 3, pp. 512–521, May–June, 2008.     

Synthesis, Characterization and Crystal Structure of [Na2(APZC)2(μ-H2O)2(μ3-H2O)]n

The synthesis and spectroscopic properties of a Na^＋ complex with ligand 3-aminopyrazine-2-carboxylic acid were described. The resulting complex was characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy and single crystal X-ray diffraction method. The title compound crystallizes in the triclinic system with space group . The crystalline structure of this compound consists of supramolecular architectures involving strong intramolecular N—H…O in pyrazine molecules and intermolecular O—H…N, O—H…O, and N—H…N hydrogen bonds between substituted pyrazine and water molecules.     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

新颖双核钐硫酚化合物[(THF)3I2Sm(m-SAr)]2 (Ar = Ph, 4-Me2NC6H4)的合成与化合物[(THF)3I2Sm(m-S-4-Me2NC6H4)]2的晶体结构

Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.     

Synthesis and characterization of the cluster complexes containing tetrahedral FeCrCo(μ3-S) cluster cores generated by isolobal displacement reactions. Crystal structures of (η-RC5H4)FeCrCo(μ3-S)(CO)8 (R=H, CO2Et) and FeCo2(μ3-S)2(CO)9

The monoanions (η⁵-RC₅H₄)(CO)₃Cr⁻ (1, R=H; 2, R=Me; 3, R=CO₂Et) reacted with tetrahedral cluster FeCo₂(μ₃-S)(CO)₉ to give single isolobal displacement products (η⁵-RC₅H₄)FeCrCo(μ₃-S)(CO)₈ (4, R=H; 5, R=Me; 6, R=CO₂Et) in 86-89% yields, whereas monoanion (η⁵-RC₅H₄)(CO)₃Cr⁻ (7, R=C(O)Me) reacted with FeCo₂(μ₃-S)(CO)₉ to afford the expected single isolobal displacement product (η⁵-RC₅H₄)FeCrCo(μ₃-S)(CO)₈ (8, R=C(O)Me) in 5% yield and an unexpected square pyramidal cluster FeCo₂(μ₃-S)₂(CO)₉ (9) in 45% yield. Similarly, the dianions [η⁵-C₅H₄CH₂(CH₂OCH₂)_nCH₂C₅H₄-η⁵][(CO)₃Cr⁻]₂ (10, n=1; 11, n=2; 12, n=3) reacted with two molecules of FeCo₂(μ₃-S)(CO)₉ to produce double isolobal displacement products [η⁵-C₅H₄CH₂(CH₂OCH₂)_nCH₂C₅H₄-η⁵][FeCrCo(μ₃-S)(CO)₈]₂ (13, n=1; 14, n=2; 15, n=3) in 32-36% yields, while treatment of dianion [η⁵-C₅H₄C(O)CH₂]₂[(CO)₃Cr⁻]₂ (16) with two molecules of FeCo₂(μ₃-S)(CO)₉ gave the unexpected square pyramidal cluster FeCo₂(μ₃-S)₂(CO)₉ (9) in 42% yield and the corresponding double isolobal displacement product [η⁵-C₅H₄C(O)CH₂]₂[FeCrCo(μ₃-S)(CO)₈]₂ (17) in 8% yield. Products 4-6, 8, 9, 13-15 and 17 were characterized by elemental analyses, IR and ¹H NMR spectroscopy, as well as for 4, 6 and 9 by X-ray diffraction techniques.     

Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(μ-S-pySH)2(PPh3)2] and [Ag2Br2(μ-S-pySH)2(PPh3)2] complexes

Reaction of silver(I) halides with PPh₃ in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag₂X₂(μ-S-pySH)₂(PPh₃)₂] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag₂S₂ cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state ³¹P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.     

［Eu2(o-ClC6H4OCH2COO)6(C12H8N2)2(H2O)2］·(CH3)2SO的晶体结构和荧光光谱

标题配合物M=1892.01,单斜晶系,空间群P2₁/c, a=1.2975(3) nm, b=2.6591(9) nm, c=1.2118(3) nm, β=96.95(1)°, Z=2, D_c=1.577 g/cm³, T=293(2)K。最终的偏离因子R=0.0583。该配合物以二聚体形式存在,通过其中的桥联羧基形成了双核分子。该分子中羧基具有桥联双齿、桥联三齿和单齿三种配位模式,Eu-Eu之间的距离为0.4019(1) nm。在77K下测得配合物中Eu(Ⅲ)离子仅有一种格位。 ⁵D₀→ ⁷F_J(J=0～2)跃迁光谱说明Eu(Ⅲ)离子格位具有C₂对称性。     

Synthesis, structure and electrochemistry of CO incorporated diruthenium metallacyclic compounds [Ru2(CO)6{μ-η:η:η:η-1,4-Fc2C5H2O}] and [Ru2(CO)6{μ-η:η:η:η-1,5-Fc2C5H2O}]

Ferrocenyl substituted ruthenium metallacyclic compounds, [Ru₂(CO)₆{μ-η¹:η¹:η²:η²-1,4-Fc₂C₅H₂O}] (1) and [Ru₂(CO)₆{μ-η¹:η¹:η²:η²-1,5-Fc₂C₅H₂O}] (2) have been synthesized and structurally characterized. Electrochemical studies for 1 and 2 and the respective quinone derivatives 3 and 4 show weak to no electrochemical coupling at the mixed-valent intermediate state which is dependent on the complex frameworks.     

[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.     

Crystal structure of [(C5Me4Et)3Rh3(μ3-Se)2](PF6)2CH3CN and [(C5Me4Et)2Rh2(μ2-Cl)3]PF6

The crystal structure of [(C₅Me₄Et)₃Rh₃(μ₃-Se)₂](PF₆)₂ and [(C₅Me₄Et)₂Rh₂(μ₂-Cl)₃]PF₆, obtained in the reaction of [(C₅Me₄Et)Rh(C₆H₆)](PF₆)₂ with ZnSe in 4M HCl under hydrothermal conditions, is determined. In agreement with the 18VE rule, the triangular cluster contains single metal-metal bonds (Rh-Rh 2.864(1) ?), whereas they are absent in the binuclear complex (Rh ...Rh 3,216(1) ?). Original Russian Text Copyright ? 2009 by P. A. Abramov, M. N. Sokolov, A. V. Virovets, and V. P. Fedin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 1, pp. 169–172, January–February, 2009.     

四核铁配合物[Fe4(NTB)4(μ2-O)2(μ4-Suc)](ClO4)6促进DNA水解

四核铁配合物[Fe₄(NTB)₄(μ₂-O)₂(μ₄-Suc)](ClO₄)₆与DNA具有较强的结合作用，结合常数k_{b达(5.9±0.4)×10⁵ L·mol^-1。该多核铁配合物由水解途径促进DNA断裂，在酸性及低离子浓度条件下的促进作用较为显著。动力学分析表明DNA水解没有明显的序列选择性，质粒DNA从超螺旋转变为切口形式符合饱和酶动力学规律，饱和速率常数ksat=0.014 min^-1。}