Metallorganische Lewis-Säuren. XLII. Carbonyl- und Nitrosyl-Komplexe von Mangan und Rhenium mit schwach koordinierten Anionen (Ph3P)2(ON)2MnX, (Ph3P)n(OC)5–nMX (M = Mn,Re; n = 1, 2; X = FBF3, OSO2CF3, OSO2F,OCORf)

Organometallic Lewis Acids. XLII. Carbonyl- and Nitrosyl Complexes of Manganese and Rhenium of Weakly Coordinated Anions (Ph₃P)₂(ON)₂MnX, (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃, OSO₂F, OCOR_f) The complexes (Ph₃P)₂(ON)₂MnX (X = FBF₃, OSO₂CF₃, OSO₂F, OCOCF₃, OCOC₃F₇) and (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃) have been obtained by reaction of (Ph₃P)₂(ON)₂MnH and (Ph₃P)_n(OC)_5–nMeMe with the corresponding acids HX or from (Ph₃P)_n(OC)_5–nReBr (n = 1, 2) with silver salts AgX, respectively. The compounds have been characterized by their IR and partially by ¹⁹F-NMR data. An efficient method for the preparation of the hydride (Ph₃P)₂(ON)₂MnH is reported.     

Apparent molar heat capacities and volumes of aqueous electrolytes: CaCl2, Cd(NO3)2, CoCl2, Cu(ClO4)2, Mg(ClO4)2, and NiCl2

We have used a flow calorimeter and a flow densimeter for measurements leading to apparent molar heat capacities and apparent molar volumes of six 21 electrolytes in aqueous solution at 25°C. Results of these measurements have been used to derive apparent molar heat capacities and volumes at infinite dilution for all six electrolytes: CaCl₂, Cd(NO₃)₂, CoCl₂, Cu(ClO₄)₂, Mg(ClO₄)₂, and NiCl₂.     

Alternativ-Liganden. XXV. Neue Chelatliganden des Typs Me2ESiMe2(CH2)2E′Me2 (E=P,As; E′=N,P, As)

Alternative Ligands. XXV. New Chelating Ligands of the Type Me₂ESiMe₂(CH₂)₂E′Me₂ (E=P, As; E′=N, P, As) Chelating ligands of the type Me₂EsiMe₂(CH₂)₂E′ Me₂, have been prepared by the following routes: Starting from Me₂Si(Vi)Cl, the compounds with E=N and E′ =N ( 1 ), P ( 2 ), As ( 3 ) are obtained in yields of 65 to 78% by aminolysis to yield Me₂NSiMe₂Vi, followed by the LiE′ Me₂ catalyzed addition of He′Me₂ to the vinyl group. The intermediates ClSiMe₂(CH₂)E′Me₂ [E′=N ( 4 ), P ( 5 ), As ( 6 )] are produced by the reactions of 1 to 3 with PhPCl₂. 5 and 6 can be prepared in a purer form by the photochemical addition of HPMe₂ and HAsMe₂, respectively, to the vinyl group of Me₂Si(Vo)Cl. 4 to 6 react with LiEMe₂, in situ prepared from n-BuLi and HEMe₂, to yield the ligands Me₂ESiMe₂(CH₂)₂E′Me₂ ( 7–12 ) (E=P, As; E′=N, P, As). The new compounds have been characterized by analytical and spectroscopic investigations (NMR, MS).     

Darstellung und Charakterisierung der Fulleren-Kokristallisate C60 · 12 C6H12, C70 · 12 C6H12, C60 · 12 CCl4, C60 · 2 CHBr3, C60 · 2 CHCl3, C60 · 2 H2CCl2

Synthesis and Characterization of the Fullerene Co-Crystals C₆₀ · 12 C₆H₁₂, C₇₀ · 12 C₆H₁₂, C₆₀ · 12 CCl₄, C₆₀ · 2CHBr₃, C₆₀ · 2CHCl₃, C₆₀ · 2H₂CCl₂ By crystallization of fullerenes from non-polar solvents (C₆H₁₂, CCl₄, CHBr₃, CHCl₃, H₂CCl₂) compounds of the following compositions were obtained: C₆₀ · 12C₆H₁₂, C₇₀ · 12C₆H₁₂, C₆₀ · 12CCl₄, C₆₀ · 2CHCl₃, C₆₀ · 2CHBr₃ and C₆₀ · 2H₂CCl₂. Lattice parameters have been determined by X-ray diffraction of powder samples; according to single-crystal examinations on C₆₀ · 12C₆H₁₂, C₆₀ · 12CCl₄ and C₆₀ · 2CHBr₃ the fullerene is orientationally disordered. C₆₀ · 12C₆H₁₂, cubic, a = 28.167(1) Å; C₇₀ · 12C₆H₁₂, cubic, a = 28.608(2) Å; C₆₀ · 12CCl₄, cubic, a = 27.42(1) Å; C₆₀ · 2CHBr₃, hexagonal, a = 10.212(1), c = 10.209(1) Å; C₆₀ · 2CHCl₃, hexagonal, a = 10.08(1), c = 10.11(2) Å; C₆₀ · 2H₂CCl₂, tetragonal, a = 16.400(1) Å, c = 11.645(7) Å.     

ChemInform Abstract: Tetrayttrium Difluoride Disilicate Orthosilicate,Y4F2[Si2O7][SiO4].

Colorless lath-shaped single crystals of the title compound are obtained from a melt of Y₂O₃, YF₃, and SiO₂ (2:5:3 molar ratio) using CsCl as a flux (evacuated silica tube, 973 K, 9 d, 10 K/h cooling rate).     

K2NaGaP2, Cs2NaGaP2, K2NaGaAs2, K2NaInP2 und K2NaInAs2, Verbindungen mit den SiS2-isosteren Polyanionen [MX4/2]3− (MGa,In; XP,As)

K₂NaGaP₂, Cs₂NaGaP₂, K₂NaGaAs₂, K₂NaInP₂ and K₂NaInAs₂, Compounds with the Polyanions [MX_4/2]^3? (M?Ga, In; X?P, As) isosteric with SiS₂ The title compounds are synthesized from stoichiometric mixtures of the elements or from Na, KP(KAs), Cs₄P₆ and MX (M?Ga, In; X?P, As) at 950K. They are isotypic and crystallize in the space group Ibam (No. 72) with Z=4. The anionic partial structure is characterized by infinite chains [MX_4/2]^3? which are isosteric to SiS₂. Vibrational spectra are measured and interpreted based on the symmetry D_4h-P(2/m 2/c)4₂/m of the isolated polymer chain [MX₂]^3?. A good agreement between observed and calculated frequencies is obtained by using a force field of the tetrameric fragment [M₄X₁₀]^18? (three four-membered M₂X₂ rings).     

ChemInform Abstract: Sc0.43(2)Rb2Mo15S19, a Partially Sc‐Filled Variant of Rb2Mo15S19.

Single crystals of the title compound are obtained from a mixture of Sc₂S₃, Rb₂MoS₄, MoS₂, and Mo (Mo crucible, 1773 K, 48 h).     

ChemInform Abstract: The Synthesis and Characterization of LaCa2Fe2GaO8.

The title compound is prepared from stoichiometric mixtures of La₂O₃, SrCO₃, Ga₂O₃, and Fe₂O₃ (flowing Ar, 1300 °C, 80 h) and characterized by neutron powder diffraction and magnetic measurements.     

Synthesis,Crystal Structure and Magnetic Properties of a 1‐D Polymer, [Cu(NITpPy)2(H2TCB)(H20)]·2H2O

A novel complex [Cu(NnpPy)₂(H_lTCB)(H₁O)]·2H₂O (NITpPy = 2‐(pyrid‐4′‐yl)‐4,4,5,5‐tetramethyl‐1, 3‐dioxoimidazoline; H₂TCB = 1, 5‐dicarboxybenzene carboxylic‐2, 4‐diacid) has been synthesized and characterized by X‐ray crystallography analysis. The crystal structure consists of infinite chains of Cu‐(NITpPy)₂(H₂O) units linked by H₂TCB ligands. The complex crystallizes in triclinic system with space group PI. Crystal data: a = 1.0594(2) nm, b = 1.3830(3) nm, c = 1.5551(3) nm, a = 67.75(3)°, β = 89.83(3)°, γ = 70.54(3)°. The variable magnetic susceptibility studies lead to magnetic coupling constant values of J₁= ?11.18 cm‐¹ (Cu—Rad) and J₂ = ?4.06 cm^?1 (Cu—Cu).     

On the interaction of Mo and Mo2 with NH3, C2H4, and C3H6

The reactivity of Mo and Mo₂ with ammonia, ethene, and propene molecules has been investigated by using Density Functional Theory. Different gradient‐corrected and hybrid exchange‐correlation functionals have been employed. Coordination modes, binding energies, geometrical structures, vibrational frequencies have been computed and compared with the available experimental counterparts. The results obtained show that the molybdenum atom is able to react with C₂H₄ and C₃H₆, and binds weakly with NH₃. The dimer Mo₂ gives a stable complexes with ammonia, ethene, and propene. For the Mo₂NH₃ complex, all the employed levels of theory give binding energies in good agreement with the experimental value, while in the case of the MoC₂H₄ system, the use of model core potentials coupled with gradient‐corrected exchange‐correlation functionals overestimates the binding energies. For MoC₃H₆, Mo₂C₂H₄, and Mo₂C₃H₆ we predict a binding energy of 14–15, 20–24, and 18–20 kcal/mol, respectively. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1557–1564, 2001     

Influence of the support on the state of nickel in the Ni/SiO2, Ni/ZrO2, and Ni/SO4/ZrO2 oxide systems studied by diffuse-reflectance IR spectroscopy

The Ni/SiO₂, Ni/ZrO₂, and Ni/SO₄/ZrO₂ systems were studied by diffuse-reflectance IR spectroscopy using CO as a probe molecule. The Ni/SiO₂ and Ni/ZrO₂ systems are similar in properties, and the state of nickel in the Ni/ZrO₂ system is determined by the specific surface area. In the Ni/SO₄/ZrO₂ system, the surface sulfur compounds affect substantially the state of nickel: Ni^δ+ species with a partial positive charge are formed due to the strong electron-acceptor properties of the sulfur compounds. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 409–413, March, 1998.     

Die Phosphide LiR2P7, Li2RP7 (R = Me3Si,Et, iPr,iBu) und alkyliert-silylierte Heptaphosphane(3)

The Phosphides LiR₂P₇, Li₂RP₇ (R = Me₃Si, Et, iPr, iBu) as well as Mixed Alkylated and Silylated Heptaphosphanes(3) Formation and properties of LiR₂P₇ and Li₂PR₇ (R = Me₃Si, Et, iPr, iBu) and their reactions with Me₃SiCl or alkylhalides yielding mixed alkylated and silylated heptaphosphanes(3) are reported. Reactions of (Me₃Si)₃P₇ and Li₃P₇. 3 DME produce mixtures of Li(Me₃Si)₃P₇, Li₂(Me₃Si)P₇ and Li₃P₇ from which pure Li(Me₃Si)₂P₇ (s, as) can be isolated by means of an extraction with toluene. Similarly, the isomers of LiR₂P₇ (R = Et, iPr, iBu) can be extracted from the mixtures obtained by reacting Li₃P₇ with alkylbromides. The (s) isomers of LiR₂P₇ in solution at about 20°C from the (as) isomers whereas the latter up to 70°C do not show any inversion. The (as) lithiumdialkylphosphides can be obtained as ether free products (red brown powder, isoluble in toluene, soluble in THF) by repeated addition of toluene and removal of the solvents; the (s) isomers decompose during the procure. In reactions of LiEt₂P₇. THF (s, as) in toluene at ?30°C with EtBr only the (s) isomer is substituted and gives Et₃P₇ (s), however on warming to 20°C by inversion of P^e a ratio of (s) : (as( = 1 : 3 is obtained. With Li(iBu)₂P₇, (s) reaction begins above ?20°C the giving both the (s) and the (as) isomer. (iBu)₃P₇ (s) is the prefered isomer at higher temperatures. Li(Me₃Si)₂P₇ (s, as) with Me₃SiCl exclusively yields (Me₃Si)₃P₇ (s). Li₂RP₇ (R = alkyl, Me₃SI) is not available. From mixtures with LiR₂P₇ and Li₃P₇, it can be isolated only after repeated cumbersome extraction of LiR₂P₇ as was shown with Li₂(iPr)P₇ as an example. Ether free LiEt₂P₇(s, as) with Me₃SiCl exclusively gives Et₂(Me₃Si)P₇ (s, as) whereas LiEt₂P₇ ? THF due to its THF content does not. Similarly, ether free Li(iBu)₂P₇ yields (iBu)₂(Me₃Si)P₇ (s, as). The compounds R(Me₃Si)₂P₇ (R = alkyl) cannot be selectively prepared neither starting from Li₂RP₇ with Me₃SiCI) nor from Li(Me₃Si)₂P₇ with RX. Such, the reaction of Li(Me₃Si)₂P₇ ? THF with EtBr in toluene at ?78°C yield a mixture of Et(Me₃Si)₂P₇ (42%), Et₂(Me₃Si)P₇ (27010), (Me₃Si)₃P₇ (29%) and Et₃P₇ (2%). (Me₃Si)₃P₇ with MeI in a molar ratio of 1 : 1 at 70°C quantitatively produces Me(Me₃Si)₂P₇ whereas already using a molar ratio of 1 : 2 also Me₃P₇ is obtained. With EtBr mixtures of Et(Me₃Si)₂P₇ and Et₃P₇ are formed. iBuBr gives iBu₃P₇, but tBuBr does not yield any tBu₃P₇.     

ChemInform Abstract: Density Functional Theory Calculations of UO2 Oxidation: Evolution of UO2‐x,U4O9‐y,U3O7, and U3O8.

DFT calculations of UO₂ oxidation indicate stable compounds U₄O_8.889, U₃O₇, and U₃O_7.333, which are based on ordering of split quad‐interstitial clusters.     

Synthesen und Eigenschaften von Tetrakis(perfluoralkyl)tellur Te(Rf)4 (Rf = CF3, C2F5, C2F5, C3F7, C4F9)

Synthesis and Properties of Tetrakis(Perfluoroalkyl)Tellurium Te(R_f)₄ (R_f = CF₃, C₂F₅, C₃F₇, C₄F₉) Te(CF₃)₄ is obtained from the reaction of Te(CF₃)Cl₂ with Cd(CF₃)₂ complexes as a complex with e. g. CH₃CN, DMF. It is a light and temperature sensitive hydrolysable liquid. The reaction with fluorides yields the complex anion [Te(CF₃)₄F]⁻, with fluoride ion acceptors the complex cation [Te(CF₃)₃]⁺. With traces of water an acidic solution is formed. Te(CF₃)₄ acts as a trifluoromethylation reagent. The reaction with XeF₂ gives hints for the formation of Ye(CF₃)₄F₂. Properties and NMR spectra are discussed. The much more stable complexes of Te(R_f)₄ (R_f = C₂F₅, C₃F₇, C₄F₉) are formed from the reaction of TeCl₄ with the corresponding Cd(R_f)₂ complexes.     

Synthesis and characteristics of novel pentanuclear complexes [(OC)3Mn(η1,η5-C5H4)Fe(CO)2(η1,η5-C5H4CO2)]2M(η5-C5H5)2 (M=Ti, Zr)

The reaction of Cp₂MCl₂ complexes (M=Ti and Zr) with 2 equiv. of (OC)₃Mn(η¹,η⁵-C₅H₄)Fe(CO)₂(η⁵-C₅H₄COONa) results in the formation of the pentanuclear complexes (OC)₃Mn(η¹,η⁵-C₅H₄)Fe(CO)₂(η⁵-C₅H₄CO₂)]₂M(η⁵-C₅H₅)₂, which are characterized by IR and¹H NMR spectroscopy and cyclic voltammetry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1055–1058, May, 1997.     

Zum Einfluß der Substituenten R = Ph,NEt2, iPr und tBu in Triphosphanen, (R2P)2P?SiMe3, und Phosphiden,Li(THF)2[(R2P)2P], auf die Bildung und Eigenschaften von Phosphinophosphiniden-Phosphoranen

Concerning the Influence of the Substituents R = Ph, NEt₂, ⁱPr, and ^tBu in Triphosphanes (R₂P)₂P? SiMe₃ and Phosphides Li(THF)₂[(R₂P)₂P] on the Formation and Properties of Phosphino-phosphinidene-phosphoranes The triphosphanes X₂P? P(SiMe₃)? PY₂ 5, 7, 9, 11, 13 and the derived phosphides Li(THF)₂[X₂P? P? PY₂] 6, 8, 10, 12, 14 were synthesized: 5 and 6 with X₂ = ⁱPr₂ and Y₂ = ^tBu₂, 7 and 8 with X₂ = Y₂ = Ph^tBu, 9 and 10 with X₂ = ^tBu₂ and Y₂ = Ph₂, 11 and 12 with X₂ = Y₂ = Ph₂, and 13 and 14 with X₂ = ^tBu₂ and Y₂ = (NEt₂)₂. The silylated triphosphanes at ?70°C in toluene with CBr₄ may yield X₂P? P?P(Br)Y₂ and X₂P? P(Br)? PY₂, and the lithiated phosphides with MeCl may yield X₂P? P?P(Me)Y₂ and X₂P? P(Me)? PY₂ depending on X and Y. The bromiated product of 5 (X₂ = ⁱPr₂, Y₂ = ^tBu₂) is the ylide ⁱPr₂P? P?P(Br)^tBu₂, and the methylated derivatives of 6 are both ⁱPr₂P? P?P(Me)^tBu₂, ^tBu₂P? P?P(Me)ⁱPr and the methylated triphosphane. Ph₂P? P?P(Br)^tBu₂ as well as the brominated triphosphane are obtained from 9 (X₂ = ^tBu₂, Y₂ = Ph₂), and similarly Ph₂P? P?P(Me)^tBu₂ and the methylated triphosphane from 10 . Compound 14 (X₂ = ^tBu₂, Y₂ = (NEt₂)₂ gives rise to the brominated ylide ^tBu₂)P? P?P(Br) · (NEt₂)₂ and to the brominated triphosphane, and on methylation to ^tBu₂P? P?P(Me)(NEt₂)₂ and to ^tBu₂P? P(Me)? P · (NEt₂)₂ (main product). The Br substituted derivatives decompose already on warming to ?30°C, while the methylated compounds are stable up to 20°C.     

2, 2′-Dihydroxyazobenzene-based fluorescent system for the colorimetric ‘turn-on’ sensing of cyanide

2, 2′-Dihydroxyazobenzene (DHAB) demonstrated high sensitivity and low selectivity toward three anions: CN⁻, CO₃²⁻, and HCO₃⁻. In the presence of Cu(II), complex DHAB-Cu(II) could give rise to enhanced fluorescence intensity by about 45-fold at 590 nm and visible red-to-reddish orange color change upon the addition of cyanide by utilizing an indirect method, while no changes were observed in the presence of other anions, including F⁻, Cl⁻, Br⁻, I⁻, H₂PO₄⁻, CH₃COO⁻, NO₃⁻, CO₃²⁻ and HCO₃⁻, and SO₄²⁻, making the DHAB-Cu(II) complex a selective and sensitive cyanide chemosensor.     

DNA Intercalating Near-Infrared Luminescent Lanthanide Complexes Containing Dipyrido[3,2-a:2′,3′-c]phenazine (dppz) Ligands: Synthesis,Crystal Structures,Stability, Luminescence Properties and CT-DNA Interaction

In order to create near-infrared (NIR) luminescent lanthanide complexes suitable for DNA-interaction, novel lanthanide dppz complexes with general formula [Ln(NO₃)₃(dppz)₂] (Ln = Nd³⁺, Er³⁺ and Yb³⁺; dppz = dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized, characterized and their luminescence properties were investigated. In addition, analogous compounds with other lanthanide ions (Ln = Ce³⁺, Pr³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Tm³⁺, Lu³⁺) were prepared. All complexes were characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction analysis of the complexes (Ln = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Eu³⁺, Er³⁺, Yb³⁺, Lu³⁺) showed that the lanthanide’s first coordination sphere can be described as a bicapped dodecahedron, made up of two bidentate dppz ligands and three bidentate-coordinating nitrate anions. Efficient energy transfer was observed from the dppz ligand to the lanthanide ion (Nd³⁺, Er³⁺ and Yb³⁺), while relatively high luminescence lifetimes were detected for these complexes. In their excitation spectra, the maximum of the strong broad band is located at around 385 nm and this wavelength was further used for excitation of the chosen complexes. In their emission spectra, the following characteristic NIR emission peaks were observed: for a) Nd³⁺: ⁴F_3/2 → ⁴I_9/2 (870.8 nm), ⁴F_3/2 → ⁴I_11/2 (1052.7 nm) and ⁴F_3/2 → ⁴I_13/2 (1334.5 nm); b) Er³⁺: ⁴I_13/2 → ⁴I_15/2 (1529.0 nm) c) Yb³⁺: ²F_5/2 → ²F_7/2 (977.6 nm). While its low triplet energy level is ideally suited for efficient sensitization of Nd³⁺ and Er³⁺, the dppz ligand is considered not favorable as a sensitizer for most of the visible emitting lanthanide ions, due to its low-lying triplet level, which is too low for the accepting levels of most visible emitting lanthanides. Furthermore, the DNA intercalation ability of the [Nd(NO₃)₃(dppz)₂] complex with calf thymus DNA (CT-DNA) was confirmed using fluorescence spectroscopy.     

ChemInform Abstract: From 1∞ [(UO2)2O(MoO4)4]6‐ to 1∞ [(UO2)2(MoO4)3(MoO5)] 6‐ Infinite Chains in A6U2Mo4O21 (A: Na,K, Rb,Cs) Compounds: Synthesis and Crystal Structure of Cs6 [(UO2)2(MoO4)3(MoO5)] .

Single crystals of the title compound are obtained from a melt of U₃O₈, MoO₃, and excess Cs₂CO₃ (Pt crucible, 950 °C, 12 h, cooling rate 5 °C/h).     

Structural Variety of Defect Perovskite Variants M3E2X9 (M = Rb,Tl, E = Bi,Sb, X = Br,I)

The compounds Rb₃Sb₂Br₉, Rb₃Sb₂I₉, Rb₃Bi₂Br₉, Rb₃Bi₂I₉, and Tl₃Bi₂Br₉ were synthesized and their crystal structures determined from single crystal X‐ray diffraction data. The compounds Rb₃Sb₂Br₉, Rb₃Sb₂I₉, and Rb₃Bi₂I₉ crystallize in the Tl₃Bi₂I₉ type of structure (space group P2₁/n, no. 14). Rb₃Bi₂Br₉ and Tl₃Bi₂Br₉ crystallize in a new but closely related type of structure (space group P2₁/a, no. 14). Both structure types feature characteristic double layers comprising corner‐sharing EX₆ octahedra. The space groups are set in a way that the stacking direction of the layers is the [001] direction. The group‐subgroup relations to cubic perovskite ABO₃ are discussed. Differences between M₃E₂X₉ types are attributed to distortions of the underlying MX₃ close packing. Depending on the atomic size ratio, the distortions are quantified by an order parameter.