The molecular structure of benzoylmethylidynetricobalt nonacarbonyl,C6H5C(O)CCo3(CO)9

The molecular structure of benzoylmethylidynetricobalt nonacarbonyl, C₆H₅C(O)CCo₃(CO)₉, has been determined by single crystal X-ray crystallography. The sample crystallized from heptane forms as monoclinic prisms of spae group P2₁/c, with a = 8.836(2), b = 14.097(10), c = 16.514(3), β = 103.37(6) and z = 2. The final R value was 0.053. The structure is regular and normal but does not aid in explaining the interesting properties of this cluster.     

The crystal and molecular structure of dicarbonylbis(diphenylethylphosphine) platinum(0) Pt(CO)2[P(C6H5)2(C2H5)]2

The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO)₂[P(C₆H₅)₂(C₂H₅)]₂, crystallizes in either of the enantiomorphous space groups P3₁21 (No. 152) and P3₂21 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 ų; p_c = 1.564 g/cm³ for Z = 3, p_m = 1.55(3) g/cm³. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3₁21) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC₂ and PtP₂ moieties make a dihedral angle of 86.0(3)°. The overall C₂ symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms.     

1-Allyl derivatives: Synthesis and crystal structures for [(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2] and [C9H7N(C3H5)Cu(NO3)2]

1-Allyl-4-aminopyridinium chloride reacts with Cu(NO₃)₂ · 3H₂O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound [(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂] (I). The crystals of compound I are monoclinic: space group P2₁/c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ?³. The direct interaction of 1-allylquinolinium nitrate with Cu(NO₃)₂ · 3H₂O in a methanolic solution in the presence of metallic copper yields crystals of compound [C₉H₇N(C₃H₅)Cu(NO₃)₂] (II). The crystals of compound II are triclinic: space group P , a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ?³. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂} _n . Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The crystal structure of compound II is built-up of the isolated L₂Cu₂(NO₃)₄ fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L₂Cu₂(NO₃)₄ fragments are additionally joined by the C-H…O hydrogen bonds. Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 458–462.     

Extraction of the [(C4H9)4N]3[Fe(SCN)6] ion-pair with chloroform: Spectrophotometric determination of iron

When excesses of ammonium thiocyanate and tetrabutylammonium chloride are added to an iron(III) solution, a water-insoluble ion-pair is formed. This compound is soluble in chloroform and other organic solvents. The variables affecting extraction with CHCl₃ are studied in order to obtain the optimal conditions and an extraction procedure is proposed. The separation of iron as a previous step to its spectrophotometric determination is studied.     

Vibrational and luminescence spectra of a new binuclear uranyl complex [(C2H5)4N]2[UO2F(NO3)2]2

The preparation, vibrational and luminescence spectra of the title compound are described. The complex has bidentate nitrate groups and bridging fluoride ions. The spectra are assigned in detail and interpreted as showing couplings between the uranyl antisymmetric stretching modes and between the nitrate modes within the dimer, the coupling energy being 17 cm^? in the former case. There is no clear evidence for electronic coupling involving the uranyl groups.     

Cu[C5H3N(CCH3=N-C6H5)2]2(PF6)2配合物的合成、晶体结构和热分解反应动力学

The title complex Cu[C₅H₃N(CCH₃=N-C₆H₅)₂]₂(PF₆)₂ has been synthesized by reaction of Schiff base C₅H₃N(CCH₃=N-C₆H₅)₂ and cupric sulfate in toluene solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 1041.85. The crystal structure belongs to triclinic system with space group P1 and cell parameters: a=12.6470(10)?, b=14.123(2)?, c=15.613(2)?;α=66.150(10)°,β=79.470(10)°,γ=78.290(10)°, V=2481.6(5)?³, Z=2, D_c=1.394Mg·m^-3 and F(000)=1064. The final R[I >2σ(I)]:R₁=0.0668, wR₂=0.1927; R(all data): R₁=0.1133, wR₂=0.2357. The Cu(Ⅱ) was coordinated by six nitrogen, at the same time the Cu(Ⅱ) formed a distorted octahedron, besides the angles and planes of this compound were discussed . The result of kinetics of the thermal decomposition indicated that the first step of it is 2 series chemical reactions, the function of machanism is f(a)=(1-a)², and the activation energy is 144.64E/kJ. CCDC: 180872.     

The reactions of 2-benzoylpyridine with [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2

The reactions of [RuHCl(CO)(PPh₃)₃] and [(C₆H₆)RuCl₂]₂ with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh₃)₂(C₅H₄NCOO)] and [RuCl₂(C₁₂H₉NO)₂] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.     

[Mo(C9H6NO)2O2]的合成和晶体结构

合成了标题化合物[Mo(C9H6NO)2(O)2](C9H6NO=8-羟基喹啉),测定了化合物的晶体结构.晶体属单斜晶系,空间群Cc,a=13.372(3),b=9.421(2),c=13.554(3)A,β=109.71(3)°,V=1607.6(8)A3.结构由直接法解出,最后可靠性因子R=0.0473,Rw=0.062.Mo原子为6配位,位于八面体的中心.两个配体氧相互处于邻位,分别与8-羟基喹啉中的N原子处于对位.     

The synthesis of phosphine derivatives of [Fe4N(CO)12]: Crystal structures of [Fe4N(CO)9(NO)(PPh3)2], [HFe4N (CO)11)PPh3)] and [(PPh3)2N][Fe4N(CO)11(PMe2Ph)]

Phosphines react with butterfly tetranuelear nitrido-iron clusters, [Fe₄N(CO)₁₂]⁻ and [Fe₄N(CO)₁₁(NO)], to give mono- and di-substituted complexes. X-Ray analyses of the title compounds showed that the phosphine ligands are bound to the wing-tip atoms.     

Synthesis, structural characterization, and magnetic properties of the metallamacrocycle [Fe6(C11H11N2O3)6(C4H9NO)6]

Abstract  

The 18-metallacrown-6 metallamacrocycle [Fe₆(pmshz)₆(C₄H₉NO)₆] has been synthesized by the self-assembly reaction of iron ions with N-substituted salicylhydrazide ligands. Six Fe(III) ions and six deprotonated N-propanoyl-4-methylsalicylhydrazide (H₃ pmshz) ligands construct a planar 18-membered ring based on Fe–N–N–Fe linkage. Because of the coordination, the ligand enforces the stereochemistry of the Fe(III) ions as a propeller shape with alternating …ΔΛΔΛ… configurations. There is a strong antiferromagnetic exchange interaction between the paramagnetic iron centers.     

Resonance Raman spectrum of the complex [(C2H5)4N] AuBr4

A resonance Raman spectrum of the complex [(C₂H₅)₄N] AuBr₄ has been observed by use of 457.9 nm Ar⁺ excitation. Three progressions in the totally symmetric stretching fundamental ν₁ (a_1g) have been observed, viz. nν₁ (as far as n = 9), ν₂ + nν₁ (as far as n = 1), and ν₄ + nν₁ (as far as n = 6). The spectroscopic constants ω₁ and x₁₁ have been determined from an analysis of the nν₁ and ν₄ + nν₁ progressions.     

Hetero- and homo-nuclear bimetallic ruthenol complexes by dehydrogenative metallacyclization of Ru(CO)3(bi-1,7-cyclooctadienyl), preparation and x-ray structure of Fe(CO)3(C16H22), RuFe(CO)6(C16H22) and Ru2(CO)6(C16H20)

The reaction of M₃(CO)₁₂ (M = Ru, Fe) with excess bi-2,7-cyclooctadienyl (C₁₆H₂₂) 1 gave a mononuclear complex M(CO)₃(1,2,1′-2′-η⁴-C₁₆H₂₂), 2a (M = Ru) or 3a (M = Fe), in good yield. Treatment of 2a with Fe₃(CO)₁₂ or reaction of 3a with Ru₃(CO)₁₂ gave the heterobimetallic complex RuFe(CO)₆(C₁₀H₂₂) consisting of a ruthenacyclopentadiene unit coordinated to an Fe(CO)₃ fragment, as confirmed by ¹H NMR and X-ray studies. The corresponding homobimetallic complex Ru₂(CO)₆(C₁₆H₂₂) was obtained from the 1:1 reaction of 2a with Ru₃(CO)₁₂, while the direct reaction of 1 with Ru₃(CO)₁₂ gave Ru₂(CO)₆(C₁₆H₂₀) preferentially with a loss of two hydrogen atoms. The pathway for formation of these bimetallic complexes was interpreted as a dehydrogenative metallacyclization followed by hydrogen transfer.     

1,2-Hydrogen abstraction: the characterization of [Li(CH3)2N(CH2)2N(CH3)2]2 [C12H8]. A dilithium complex obtained by the 1,2 deprotonation of acenaphthylene

The reaction of n-butyllithium chelated to N,N,N′,N′-tetramethylethylenediamine (TMEDA) with acenaphthene results in 1,2-hydrogen abstraction to give the dilithio complex of acenaphthylene, [Li(CH₃)₂N(CH₂)₂N(CH₃)₂]₂[C₁₂H₈]. This compound was isolated as a crystalline product and characterized by single crystal X-ray crystallography. [Li(CH₃)₂N(CH₂)₂N(CH₃)₂]₂[C₁₂H₈] crystallizes with a unit cell of a = 23.164(10), b = 25.609(10) and c = 8.495(6) Å in the orthorhombice space group Fdd2. The calculated density is 1.04 g cm^?3 for 8 molecules per unit cell. The observed density is 1.03(4) g cm^?3. 1412 unique reflections were measured on a full circle X-ray diffractometer. The light atom, acentric structure was solved by the symbolic addition technique and refined by full matrix least squares to R₁ = 0.058 and R₂ = 0.056.The acenaphthylene fragment is nearly planar. The effect of charge transfer is evidenced in the short C(3)C(4) bond distance of 1.30(3) Å and the lengthening of the C(1)C(2) bond length from the localized olefinic bond distance of 1.34 to 1.42(2) Å. The two LiTMEDA fragments are coordinated to both sides of the five membered carbon atom ring of the acenaphthylene group.     

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

A new chemical oxidant [N(4-C₆H₄Br)₃][B(C₆F₅)₄], was prepared and used to synthesize [Fe(C₅H₅)₂][B(C₆F₅)₄]. The crystal structure of [Fe(C₅H₅)₂][B(C₆F₅)₄] was determined.     

Effect of ligands on the thermolysis of the double complexes [Co(NH3)6]2C2O4[Cu(C2O4)2]2 and [Co(NH3)6]Cl[Cu(C7H4O3)2]

The thermolysis of the complexes [Co(NH₃)₆]₂C₂O₄[Cu(C₂O₄)₂]₂ (I) and [Co(NH₃)₆]Cl[Cu(C₇H₄O₃)₂] (II) in air and hydrogen at 200, 350, and 500°C and the composition and properties of the thermolysis products are considered. The oxidative thermolysis of the complexes yields mixtures of cobalt and copper oxides, including mixed ones. The reductive thermolysis of the complexes yields a Co + Cu bimetallic powder in the case of compound I and a Co + Cu + C powder in the case of compound II. The thermal behavior of the complexes is governed by the nature of the ligand coordinated to the copper atom. The observed data are explicable in terms of the properties of this ligand. The chemistry of the oxidative and reductive thermolysis is discussed. Original Russian Text ? D.P. Domonov, S.I. Pechenyuk, N.L. Mikhailova, A.T. Belyaevskii, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 7, pp. 1104–1110.     

Synthesis and Structure of a New Organic-Inorganic Framework with Tetranuclear Clusters, [Co4(OH)2(H2O)2](C4H11N2)2[C6H2(COO)4]2·3H2O

A new hybrid organic-inorganic three-dimensional compound, [Co₄(OH)₂(H₂O)₂](C₄H₁₁N₂)₂[C₆H₂(CO₂)₄]₂·3H₂O 1, has been synthesized via hydrothermal reactions and characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and magnetic techniques. Compound 1 crystallizes in the monoclinic space group P2₁/n (no. 14) with a=6.3029(9) Å, b=16.413(2) Å, c=17.139(2) Å, β=98.630(2)°, V=1735.0(4) ų, Z=2. Compound 1 contains tetranuclear Co₄(μ₃-OH)₂(H₂O)₂ clusters that are inter-linked by pyromellitate bridging ligands into a three-dimensional structure containing one-dimensional tunnels along the a-axis with water and pendant monoprotonated piperazine molecules in the center. The variable temperature magnetic susceptibility was measured from 2 to 300 K at 5000 Oe showing a predominantly anti-ferromagnetic interaction in 1, and the field dependence of magnetization was measured at 2, 5, 15, and 20 K indicating the competition of magnetic interactions in the tetranuclear centers.     

Solubility of trans-Co2(CO)6 [3,5-bis(CF3)C6H3P(i-C3H7)2] in dense carbon dioxide

The title compound (1) was prepared by the reaction of 3,5-bis(CF₃)C₆H₃P(i-C₃H₇)₂ (L1) and Co₂(CO)₈. Its solubility in supercritical carbon dioxide was measured at varying temperatures and pressures using a modified analytical extraction device. Solubility data were determined in the temperature and pressure ranges between 40 and 70 °C and between 100 and 300 bar, respectively. The solubility of 1 is lower compared to (p-CF₃C₆H₄)₃P, but much higher than for transition metal complexes bearing phosphines without fluorinated substituents.     

Die thermische reaktion von C5H5(CO)2FeNa mit benzimidchloriden C6H5(Cl)CNR

η⁵-C₅H₅(CO)₂FeNa reacts with the benzimide chlorides C₆H₅(Cl)CNR (R  CH(CH₃)₂, C₆H₅) in boiling THF to give the η¹-iminoacyl complexes η⁵-C₅H₅ (CO)₂Fe[η¹-C(C₆H₅)NR]. Alternatively, the new Fe complexes [η⁵-C₅H₅(CO)Fe$\text{C(C}{}_6\text{H}{}_5\text{)N(CH}{}_3\text{)C(C}{}_6\text{H}{}_5\text{)N}$CH₃PF₆ (IV) and [η⁵-C₅H₅(CO)₂FeC(C₆H₅)N(CH₃)C(C₆H₅)NCH₃]PF₆ (V) are formed under the same conditions, if R  CH₃. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η⁵-C₅H₅(CO)₂FeC(C₆H₅)NHCH₃]PF₆ (VII). Reaction of η⁵-C₅H₅(CO)₂ with N-benyzylbenzimido chloride yields η⁵-C₅H₅(CO)₂FeCH₂C₆H₅ as the only isolated product.     

Synthesis and crystal structures of (C8h8)Nd(C5H9C5H4) (THF)2 and [(C8H8)Gd(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)2]

LnCl₃ (Ln=Nd, Gd) reacts with C₅H₉C₅H₄Na (or K₂C₈H₈) in THF (C₅H₉C₅H₄ = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C₅H₉C₅H₄)LnCl₂(THF)_n (orC₈H₈)LnCl₂(THF)_n], which further reacts with K₂C₈H₈ (or C₅H₉C₅H₄Na) in THF to form the litle complexes. If Ln=Nd the complex (C₈H₈)Nd(C₅H₉C₅H₄)(THF)₂ (a) was obtained: when Ln=Gd the 1 : 1 complex [(C₈H₈)Gd(C_%H₉)(THF)][(C₈H₈)Gd(C₅H₉H₄)(THF)₂] (b) was obtained in crystalline form.

The crystal structure analysis shows that in (C₈H₈)Ln(C₅H₉C₅H₄)(THF)₂ (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η⁵), cyclooctatetraenyl (η⁸) and two oxygen atoms from THF are coordinated to Nd³⁺ (or Gd³⁺) with coordination number 10.

The centroid of the cyclopentadienyl ring (Cp′) in C₅H₉C₅H₄ group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd³⁺ (or Gd³⁺). In (C₈H₈)Gd(C₅H₉C₅H₄)(THF), the cyclopentyl-cyclopentadienyl (η⁵), cyclooctatetraenyl (η⁸) and one oxygen atom are coordinated to Gd³⁺ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd³⁺, which is almost in the plane (dev. -0.0144 Å).     

Reactivity of 2,3-bis(2-pyridyl)pyrazine with [Re2(CO)8(CH3CN)2]: Molecular structures of [Re2(CO)8(C14H10N4)] and [Re2(CO)8(C14H10N4)Re2(CO)8]

The reaction of the labile compound [Re₂(CO)₈(CH₃CN)₂] with 2,3-bis(2-pyridyl)pyrazine in dichloromethane solution at reflux temperature afforded the structural dirhenium isomers [Re₂(CO)₈(C₁₄H₁₀N₄)] (1 and 2), and the complex [Re₂(CO)₈(C₁₄H₁₀N₄)Re₂(CO)₈] (3). In 1, the ligand is σ,σ′-N,N′-coordinated to a Re(CO)₃ fragment through pyridine and pyrazine to form a five-membered chelate ring. A seven-membered ring is obtained for isomer 2 by N-coordination of the 2-pyridyl groups while the pyrazine ring remains uncoordinated. For 2, isomers 2a and 2b are found in a dynamic equilibrium ratio [2a]/[2b]  =  7 in solution, detected by ¹H NMR (−50 °C, CD₃COCD₃), coalescence being observed above room temperature. The ligand in 3 behaves as an 8e-donor bridge bonding two Re(CO)₃ fragments through two (σ,σ′-N,N′) interactions. When the reaction was carried out in refluxing tetrahydrofuran, complex [Re₂(CO)₆(C₁₄H₁₀N₄)₂] (4) was obtained in addition to compounds 1-3. The dinuclear rhenium derivative 4 contains two units of the organic ligand σ,σ′-N,N′-coordinated in a chelate form to each rhenium core. The X-ray crystal structures for 1 and 3 are reported.