Cyclopentadienyl-Liganden mit hydrophilen tentakeln

Cyclopentadienyl ligands bearing hydrophilic tentacles are obtained by treating Cp′SiMe₂Cl (Cp′ Cp or C₅Me₄H) with H(OCH₂CH₂)_nOMe (n = 2 or 3) in the presence of pyridine; the products Cp′SiMe₂(OCH₂CH₂)_nOMe can be deprotonated by potassium in toluene. Reaction of the potassium salt of CpSiMe₂(OCH₂CH₂)₂OMe with Me₂SiCl₂ yields C₅H₄(SiMe₂Cl)(OCH₂CH₂)₂OMe, which can be treated with H(OCH₂CH₂)₂OMe to give C₅H₄[(OCH₂CH₂)₂OMe]₂.     

Neue Metallatrane von Übergangselementen: Chloro- und Cyclopentadienyltitatran und Chloro- und Acetatozirconatran

New Metallatranes of Transition Elements: Chloro- and Cyclopentadienyltitatrane and Chloro- and Acetatozirconatrane Synthesis and characterization of chloro- and cyclopentadienyltitatrane, [ClTi(OCH₂CH₂)₃N]₂ and [CpTi(OCH₂CH₂)₃N], and of chloro- and acetatozirconatrane, [ClZr(OCH₂CH₂)₃N]_n and [CH₃CO₂Zr(OCH₂CH₂)₃N]₂, as well are described as new types of metallatranes of transition elements.     

Syntheses,spectroscopic study and crystal structures of some new <Emphasis Type="Italic">N</Emphasis>-benzoylphosphoric triamides

The reaction of N-benzoylphosphoramidic dichloride with amines afforded some new N-benzoylphos-phoric triamides with formula C₆H₅C(O)NHP(O)(X)₂, X=NH–CH(CH₃)₂ (1), NH–CH₂–CH(CH₃)₂ (2), NH–CH₂–CH(OCH₃)₂ (3), N(CH₃)[CH₂CH(OCH₃)₂] (4) and N(CH₃)(C₆H₁₁) (5) that were characterized by ¹H,¹³C,³¹P NMR, IR spectroscopy and elemental analysis. The structures have been determined for compounds 4 and 5 by X-ray crystallography. These compounds contain one amidic hydrogen atom and form centrosymmetric dimmers via intermolecular –P–O⋯H–N–hydrogen bonds besides weak C–H⋯O hydrogen bonds that lead to three-dimensional polymeric clusters in the crystalline lattice.     

Heteropoly Complexes Na0.5Cs2 ? x[H0.5 ? xM

Crystals of novel heterepoly complexes (HPC) Na_0.5Cs_{2 − x} [H_{0.5 − x} M _x ^II X^III(OH)₆Mo₆O₁₈] · 7−8H₂O (M^II = Fe, Mn; X^III = Cr, Al) are synthesized. Crystal structures of the complexes Na_0.5Cs_{2 − x} [H_{0.5 − x} Fe_xCr(OH)₆Mo₆O₁₈] · 7H₂O (I) (x = 0.19) and Na_0.5Cs_{2 − x} [H_{0.5 − x} Mn_xAl(OH)₆Mo₆O₁₈] · 8H₂O (II) (x = 0.22) are determined (space group Pbcn, Z = 8, a = 23.023(4) Å, b = 22.064(4) Å, c = 11.606(3) Å, V = 5895.66 ų for I and a = 22.972(9) Å, b = 22.002(8) Å, c = 11.543(5) Å, V = 5834.18 ų for II, respectively). The [X^III(OH)₆Mo₆O₁₈]³⁻ ligands were found to be coordinated in monodentate fashion to M atoms due to the participation of a terminal O atom of the cis-MoO₂ group in coordination with the Fe and Mn atoms, which was confirmed by IR data. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 9, 2005, pp. 663–676. Original Russian Text Copyright ? 2005 by Gavrilova, Molchanov.     

Synthesis, structure, and properties of [RuNO(NH3)4OH][PtCl4] and [RuNO(NH3)4OH][PdCl4]

Double complex [RuNO(NH₃)₄OH][PtCl₄] (I) and [RuNO(NH₃)₄OH][PdCl₄] (II) salts have been prepared and explored with TGA, IR spectroscopy, powder and single crystals X-ray diffraction. Crystal phases of I and II are isostructural (space group Cmc2₁) and have the following crystal chemical characteristics: a = 8.106 Å, b = 18.190(3) Å, c = 8.097 Å, V = 1194.0 ų, Z = 4, ρ_calc = 3.077 g/cm³ (I), and a = 8.116 Å, b = 18.135 Å, c = 8.062 Å, V = 1186.5 ų, Z = 4, ρ_calc = 2.600 g/cm³ (II). The product of thermal decomposition of I in inert and hydrogen atmospheres is a substitution solid solution Pt_0.5Ru_0.5 with the parameter of the FCC unit cell a = 3.856(3) Å. Thermolysis of II affords two-phase mixtures of limited solid solutions of the metals featuring Ru-based HCP and Pd-based FCC cells. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No.1, pp.114–121, January–February, 2007.     

Crystal structures of the octahedral rhenium cluster compexes Cs4[Re6S8(OH)6]·6H2O and Cs4[Re6Se8(OH)6]·8H2O

The salts Cs₄[Re₆S₈(OH)₆]·6H₂O (1) and Cs₄[Re₆Se₈(OH)₆]·8H₂O (2) were obtained by the reactions of Re₆S₈Br₂ and Re₆Se₈Br₂ with a CsOH melt with further solution of the products in water and crystallization of 1 and 2 from the aqueous solutions. The structure of the compounds was established by X-ray single crystal diffraction analysis. Compound 1 crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 14.175(2) Å, b = 11.321(2) Å, c = 17.503(2) Å, V = 2808.5(7) ų, Z = 4, d _calc = 5.003 g/cm³; compound 2 crystallizes in the triclinic space group with unit cell parameters a = 9.020(4) Å, b = 9.127(4) Å, c = 10.289(4) Å, α = 79.589(7)°, β = 75.829(7)°, γ = 72.186(7)°, V = 776.8(6) ų, Z = 1, d _calc = 5.402 g/cm³. Original Russian Text Copyright ? 2007 by K. A. Brylev, Yu. V. Mironov, S.-J. Kim, and V. E. Fedorov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 6, pp. 1183–1188, November–December, 2007.     

Reactions of Ru3(CO)12 with Ene-yne and Alkoxy-silyl Functionalized Compounds. The Crystal Structure of (μ-H)Ru3(CO)9[μ3-η2-HC=N(CH2)3Si(OEt)3]

Ru₃(CO)₁₂ has been reacted with the compounds hex-1-en-3-yne [EtC≡CCH=CH₂], 2-methyl-hex-1-en-3-yne [EtC≡CC(=CH₂)CH₃] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)₃Si(CH₂)₃NCO] and the compound tb [(EtO)₃Si(CH₂)₃NHC(=O)OCH₂C≡CCH₂OC(=O)NH(CH₂)₃Si(OEt)₃] in hydrocarbon solution. Some reactions in CH₃OH/KOH solution (followed by acidification) have also been performed. The main products of the reactions with ene-ynes are the clusters Ru₃(CO)₆(μ-CO)₂L₂ (L = C₆H₈, C₇H₁₀) and their demolition products, the “ferrole” Ru₂(CO)₆L₂ complexes. One of the isomers of Ru₃(CO)₆(μ-CO)₂L₂, and Ru₂(CO)₆L₂ (L = C₇H₁₀) have been reacted with vinyl-triethoxysilane [(EtO)₃SiCH=CH₂]: these reactions did not afford complexes containing new carbon–carbon bonds or triethoxy-silyl groups. Only polymerization of vinyl-triethoxysilane occurred. The reactions of Ru₃(CO)₁₂ with triethoxysilyl-propyl-isocyanate and tb (in the presence of Me₃NO) lead to the same products, that is the isomeric complexes (μ-H)Ru₃(CO)₉[C=N(H)(CH₂)₃Si(OEt)₃] with a “perpendicular” ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃] with a “parallel” ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part of a study on the synthesis of inorganic-organometallic materials through sol–gel techniques. This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday.     

A Theoretical Study of Amine Bonding in Titanium Alkoxide Adducts

Summary. DFT calculations were carried out on Ti₂(OCH₃)₈ (NH₂CH₃)₂ and Ti₂(OCH₃)₈(NH₃)₂, which are model compounds for the previously isolated amine adducts Ti₂(OR)₈(NH₂ R′)₂. The calculations show that the Ti–N bond strength is weak; however, coordination of the amine to the metal center is supported by a N–H···O hydrogen bond of the amine with the neighboring alkoxo ligand. The Ti–N interaction is purely σ in nature, while the Ti–O interactions include both σ and π contributions. The lowest unoccupied molecular orbitals are mainly localized on Ti t_2g-like orbitals.     

1,2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质

通过配体1,2-环己二胺缩邻香兰素（H₂L）和不同的镱盐反应,合成了4个镱稀土配合物[Yb（H₂L）₂]（ClO₄）₃·2CH₃OH·H₂O（1）,[Yb₄（L）₄（NO₃）₂（H₂O）₂]（PF₆）₂·4CH₃CN（2）,[Yb₄（L）₄（H₂O）₂Cl₂]（PF₆）₂·2CH₂Cl₂·2H₂O（3）和[Yb₄（L）₄（NO₃）₂（H₂O）₂][Yb（NO₃）₃（H₂O）₂（CH₃OH）]（NO₃）₂ ·4CH₂Cl₂·6CH₃OH（4）。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

Diastereoselective addition of organomanganese compounds to α-alkoxysubstituted propanals

Reactions of organomanganese compounds R¹MnI (R¹ = Ph, 4-MeC₆H₄-, Me, Bu,n-C₇H₁₅, BuC=C, PhOC), prepared from R¹Li and Mnl₂ in Et₂O, with aldehydes MeCH(OR²)CHO (R² = CH₂Ph, CH₂OMe, CH₂OCH₂Ph) affordthreo-alcohols MeCH(OR²)CH(OH)R¹ with high diastereoselectivity. The interactions of phenylmanganese derivatives PhMnX (X = Cl, Br, I), Ph₂Mn, and Ph₃MnLi with 2-benzyloxypropanal were used as examples for studying the influence of reagent and solvent nature on addition diastereoselectivity.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 178–181, January, 1993.     

Reactions of Co2(CO)6(RC≡CR′) (RC2R′—hydroxy- or alkoxysilyl-alkynes) with tetraethyl-orthosilicate

Co₂(CO)₈ has been reacted with but-2-yn-1,4-diol (BUD) and the reactivity of the resulting complex Co₂(CO)₆(HOCH₂C≡CCH₂OH) (complex 1) is discussed. Complex 1 has been reacted with all the components used in the synthesis of sol-gel materials based on tetraethyl-orthosilicate (TEOS) with the aim at obtaining evidences for the processes occurring during the formation of inorganic-organometallic sol-gel materials containing BUD. Reaction pathways are discussed. BUD and complex 1 have also been reacted with 3-(triethoxysilyl)propyl isocyanate (TSI); the new ligand [(EtO)₃Si(CH₂)₃NHC(— O)OCH₂C≡CCH₂OC(—O)NH(C H₂)₃Si(OEt)₃] (TB) and the complex Co₂(CO)₆[(EtO)₃Si(CH₂)₃NHC(—O)OCH₂C≡CCH₂OC(—O)NH(CH₂)₃Si(OEt)₃] (11) have been obtained; these were characterized by means of spectroscopic techniques and mass spectrometry. Reactions of ligand TB and of complex 11 with TEOS have been performed. “Condensation” reactions of ligand TB (with TB) and of complex 11 (with complex 11) have also been attempted. Solid, amorphous materials were obtained: these were characterized by means of IR-Raman, SEM microscopy and XRD on powders.     

Syntheses,crystal structures and thermal behavior of three Mn(II) complexes with 4-acyl pyrazolone derivatives

Three new manganese complexes, [Mn(PPeAP-INH)(CH₃OH)₂]_n(CHCl₃) (1) [PPeAP-INH=N-(1-phenyl-3-phenylethyl-4-ethylene-5-pyrazolone isoniazid, INH = isoniazid], [Mn₂(PM4MbP-INH)₂(CH₃OH)₄](CH₃OH) (2·CH₃OH), [PM4MbP-INH=N-(1-phenyl-3-methyl-4-(p-methylbenzoylene)-5-pyrazolone) isoniazid)] and [Mn₂(PPePeP-INH)₂(CH₃OH)₄] (3) [PPePeP-INH=N-(1-phenyl-3-phenylethyl-4-phenylethylene-5-pyrazolone) isoniazid] have been prepared, aiming at the formation of extended coordination polymer with Mn(II) ions. Formation of the corresponding manganese-ligand complexes has been monitored and characterized by chemical and spectroscopic techniques. X-ray diffraction analyses of available single crystals revealed 1D polymeric patterns of supramolecular system. Among them, the dimers of 2 and 3, bridged by two methanol molecules, are extended by hydrogen bond of O–H···N to form the 1D chain. In these three new complexes which are all octahedral coordination environments, the N(5) atom of the pyridine heterocycles plays a very important role in building the bridged polymeric chain.     

Synthesis and characterization of ferrocenylalkoxygermatranes and crystal structures of FcCH2OGe (OCH2CH2)3N and FcCH(CH3)OGe(OCH2CH2)3N1

Germatranes bearing a ferrocenylalkoxyl moiety have been obtained by the reaction of HOGe(OCH₂CH₂)₃N with various ferrocenyl alcohols. A convenient new synthesis method of FcCH₂OGe(OCH₂CH₂)₃N was reported. FcCH₂OGe(OCH₂CH₂)₃N was prepared in 93% yield when FcCH₂OH reacted with HOGe(OCH₂CH₂)₃N in chloroform at room temperature in the presence of molecular sieves (3 Å) as a dehydrating agent. All compounds were characterized by elemental analysis, ¹H NMR and IR spectroscopy. The molecular structures of FcCH₂OGe(OCH₂CH₂)₃N and FcCH(CH₃)OGe(OCH₂CH₂)₃N have been determined by X‐ray diffraction. The antitumor activities of FcCH₂OGe(OCH₂CH₂)₃N and p‐FcC₆H₄CH₂OGe(OCH₂CH₂)₃N were determined. Copyright © 2005 John Wiley & Sons, Ltd.     

Manganese(II) complexes of hydrazone based NNO-donor ligands and their catalytic activity in the oxidation of olefins

The reaction between tridentate NNO donor hydrazone ligands, (E)-2-cyano-N′-(phenyl(pyridin-2-yl)methylene)acetohydrazide (HL¹) and (E)-2-cyano-N′-(1-(pyridin-2-yl)ethylidene)acetohydrazide (HL²), with MnCl₂·4H₂O in methanol resulted in [Mn(HL¹)Cl₂(CH₃OH)] (1) and [Mn(HL²)Cl₂(CH₃OH)] (2). Molecular structures of the complexes were determined by single-crystal X-ray diffraction. All of the investigated compounds were further characterized by elemental analysis, FT-IR, TGA, and UV–Vis spectroscopy. These complexes were used as catalysts for olefin oxidation in the presence of tert-butylhydroperoxide (TBHP) as an oxidant. Under similar experimental conditions with equal manganese loading, the presence of [Mn(HL²)Cl₂(CH₃OH)] (2) resulted in higher conversion than [Mn(HL¹)Cl₂(CH₃OH)] (1).     

Liquid Densities and Excess Molar Volumes for Binary Systems (Ionic Liquids + Methanol or Water) at 298.15, 303.15 and 313.15 K,and at Atmospheric Pressure

Binary excess molar volumes, V _m ^E, have been evaluated from density measurements, using a vibrating tube densimeter over the entire composition range for binary liquid mixtures of ionic liquids 1-ethyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [EMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻ or 1-butyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [BMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻ or 1-methyl-3-octyl-imidazolium diethyleneglycol monomethylethersulphate [MOIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻+methanol and [EMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻+water at 298.15, 303.15 and 313.15 K. The V _m ^E values were found to be negative for all systems studied. The V _m ^E results are explained in terms of intermolecular interactions and packing effects. The experimental data were fitted by the Redlich-Kister polynomial.     

1，2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质

通过配体1,2-环己二胺缩邻香兰素（H2L）和不同的镱盐反应,合成了4个镱稀土配合物[Yb（H₂L）₂]（ClO₄）₃·2CH₃OH·H₂O（1）,[Yb₄（L）₄（NO₃）₂（H₂O）₂]（PF₆）₂·4CH₃CN（2）,[Yb₄（L）₄（H₂O）₂Cl2]（PF₆）₂·2CH₂Cl₂·2H₂O（3）和[Yb₄（L）₄（NO₃）₂（H₂O）₂][Yb（NO₃）₃（H₂O）₂（CH₃OH）]（NO₃）₂·4CH₂Cl₂·6CH₃OH（4）。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

Heterometallic Alkoxide Complexes of Variable Composition—A New Way to Ultrafine Powders of Metal Alloys

The anodic oxidation of Re metal in MeOH (Me = CH₃) provides a mixture of Re₂O₃(OMe)₆ and Re(V) oxoalkoxides that on storage or on heating give insoluble and air stable Re₄O_6–y (OMe)_12+y (I). I can be also obtained by reaction of Re₂O₇ with MeOH. In the presence of MoO(OMe)₄, a heterometallic complex ReMoO₂(OMe)₇(II) is formed as intermediate, the final product being Re_4–x Mo _x O_6–y (OMe)_12+y (III). The electrosynthesis in the presence of WO(OMe)₄ gives Re_4–x W _x O_6–y (OMe)_12+y (IV) only at very high Re : W ratios in solutions and the W content varies in one and the same sample. The dissolution of Re₂O₇ in the solutions of MO(OMe)₄, M = Mo,W in toluen on reflux yields Re_4–x M _x O_6–y (OMe)_12+y with uniform Re : M distribution. The cocrystallization of MoO(OMe)₄ and WO(OMe)₄ yields (Mo,W)O(OMe)₄ (V) with almost uniform Mo : W distribution. The thermal decomposition of II and III in inert atmosphere gives fine powder of the (Re,Mo)O₂ phase. The reduction with hydrogen gas converts II and III into an ultrafine powder of Re–Mo alloy at temperatures below 400°C. The latter can be sintered into compact metal at 800–900°C.     

Synthesis of polyphosphazenes bearing alkoxyethoxy and trifluoroethoxy groups

The synthesis of various phosphoranimines including (CH₃OCH₂CH₂O) (CF₃CH₂O)₂P?N? Si(CH₃)₃, (CH₃OCH₂CH₂OCH₂CH₂O) (CF₃CH₂O)₂P?N? Si (CH₃)₃, (CH₃OCH₂CH₂O)₂(CF₃CH₂O) P?N? Si(CH₃)₃, and (CH₃OCH₂CH₂OCH₂CH₂O)(CF₃CH₂O) P?N? Si(CH₃)₃ via the Staudinger reaction of (CH₃)₃SiN₃ with the suitably substituted phosphite is reported. These monomers were polymerized using tetra-n-butylammonium fluoride and N-methylimidazole in various solvents at several temperatures. In situ ³¹P-NMR kinetic studies and M_n versus time studies were also performed for the monomers to understand the propagation mechanism. © 1994 John Wiley & Sons, Inc.     

Synthesis and structure of [Ni(dien)2]3[W4S4(CN)2]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O

[Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O and [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O were obtained by evaporating water-ammonia solutions containing K₆[W₄S₄(CN)₁₂]·2H₂O·2CH₃OH, diethylene triamine, and NiCl₂·6H₂O or CuCl₂·6H₂O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)₂]₃[W₄S₄(CN)₁₂]·20H₂O are: triclinic system, , a = 14.671(2) Å, b = 16.448(3) Å, c = 19.814(3) Å, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) ų, Z = 2; for the complex [Cu(dien)(Hdien)]₂[W₄S₄(CN)₁₂]·8H₂O: monoclinic system, C2/c, a = 37.4290(1) Å, b = 17.7370(1) Å, c = 25.7370(2) Å, β = 105.3840(2)°, V = 16474.02(16) ų, Z = 12. Original Russian Text Copyright ? 2005 by I. V. Kalinina, D. G. Samsonenko, Z. A. Starikova, A. A. Korlyukov, J. Lipkowski, V. P. Fedin, and M. Yu. Antipin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 139–148, January–February, 2005.     

Hydrosilylation of unsaturated compounds with 5-dimethylsilylfurfural diethyl acetal

Hydrosilylation of terminal acetylenes, HC≡CR (R = CMe₃,n-C₇H₁₅, SiMe₃, Ph, COOEt, CH₂N(CH₂)₄, and CH₂N(CH₂)₅) with 5-dimethylsilylfurfural diethyl acetal (1) gives a mixture of products of bothtrans-β- and α-addition. When R = CMe₃ or SiMe₃, the reaction proceeds regio- and stereospecifically to give only thetrans-β-derivatives. The formation of β-adducts is favored by pronounced electron-donating substituents and steric hindrance at the C_α atom. Terminal alkenes, H₂C=CHR (R = CH₂CN, CH₂N(CH₂)₄, CH₂N(CH₂)₅, SiMe₃, SiMe(α-furyl)₂, SiMe₂(α-furyl), SiMe₂(α-thienyl), and SiMe₂(5-chloro-2-thienyl)), react with silane1 to give only the products of β-addition; the reaction of1 with H₂C=CHCH₂NHC₆H₁₃-n affords a mixture of β- and α-adducts in a ratio of 1.8∶1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1784–1788, October, 1993.