Excitonic Bands in the Spectra of Some Organic-Inorganic Hybrid Compounds Based on Metal Halide Units

Summary.  The optical absorption, photoluminescence, and photoconductivity spectra of some compounds of the formulas [R(CH₂) _n NH₃] _x M _y X _z , [R(CH₂) _n NH(CH₃)₂] _x M _y X _z , [R(CH₂) _n S(CH₃)₂] _x M _y X _z , [R(CH₂) _n SC(NH₂)₂] _x M _y X _z , and [R(CH₂) _n SeC(NH₂)₂] _x M _y X _z (R = organic residue; M = Bi(III), Pb(II), Sn(II), Cu(I), Ag(I) etc; X = I, Br, Cl; n, x, y, z = 0, 1, 2, 3, …) are briefly reviewed, and some new results are reported. The position, intensity, and shape of the excitonic bands depend on the dimensionality and size of the inorganic network as well as on the nature of the M, X, R, and onium moieties. Received June 23, 2000. Accepted August 1, 2000     

Al,B, and F doped LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> as cathode material of lithium-ion batteries

A series of the mixed transition metal compounds, Li[(Ni_1/3Co_1/3Mn_1/3)_1–x-y Al _x B _y ]O_2-z F _z (x = 0, 0.02, y = 0, 0.02, z = 0, 0.02), were synthesized via coprecipitation followed by a high-temperature heat-treatment. XRD patterns revealed that this material has a typical α-NaFeO₂ type layered structure with R3^- m space group. Rietveld refinement explained that cation mixing within the Li(Ni_1/3Co_1/3Mn_1/3)O₂ could be absolutely diminished by Al-doping. Al, B and F doped compounds showed both improved physical and electrochemical properties, high tap-density, and delivered a reversible capacity of 190 mAh/g with excellent capacity retention even when the electrodes were cycled between 3.0 and 4.7 V.     

Using intercalation compounds of aluminum hydroxide for syntheses of nanoscale systems

Routes for synthesizing intercalation compounds of aluminum hydroxide [M_xAl_y(OH)_z]_n X · pH₂O (M=Li, Mg, Ni, Co, …) are suggested, and application of these schemes to syntheses of nanoscale systems is examined. It is shown that nanoscale systems varying in composition, structure, and morphology may be obtained according to the nature of anion X and reaction conditions. Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences (Novosibirsk). Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 3, pp. 453–459, May–June, 1998.     

Organosilicon Amine Gels Based on 3-Aminopropyltriethoxysilane, Cobalt(II) or Chromium(III) Clorides, and Triethoxysilane

Organosilicon gels [Co(NH₂R²)₂Cl₂] and [Cr(NH₂R²)₃Cl₃], containing a diaminodichloride complex of cobalt(II) and triaminotrichloride complex of chromium(III) (R² = CH₂CH₂CH₂SiO(OEt)), were synthesized by the hydrolysis of complexes [Co(NH₂R¹)₂Cl₂] (I) and [Cr(NH₂R¹)₃Cl₃] (II) incorporating peripheral triethoxysilyl groups (R¹ = CH₂CH₂CH₂Si(OEt)₃). The coprecipitated [Co(NH₂R²)₂Cl₂] · 4NH₂R³, [Cr(NH₂R²)₃Cl₃] · 6NH₂R³, [Co(NH₂R²)₂Cl₂] · 2SiO₂, and [Cr(NH₂R²)₃Cl₃] ·xSiO₂ · (3 – x)SiHO_1.5 (R³ = CH₂CH₂CH₂SiO_1.5) gels were obtained by cohydrolysis of complexes I and II with 3-aminopropyltriethoxysilane or triethoxysilane. Interaction with SiH(OEt)₃ is accompanied by the decomposition of silicon hydride groups and the formation of tetraethoxysilane derivatives. The heating of dry gels in a flow of argon or oxygen to 600° results in the formation of amorphous silica having a specific surface area 2–467 m²/g and containing crystalline metals, their chlorides, oxides, silicates, or carbides.     

Synthese „anorganischer”︁ Tintenfisch-Moleküle. II

Synthesis of “Inorganic” Pode-type Molecules. II The reaction of the amino compounds Me_yB? NMe₂ (B ? As, y ? 2; B ? Si, y ? 3) with 1, n-dioles results in the formation of the compounds HO(CH₂)_nOBMe_y. These compounds can be used as the arms of pode-type molecules Me_xA[? O(CH₂)_nOBMe_y]_z with A ? Si, As. The influence of A, B, n, and z in the rearrangement of these molecules is examined. A second type of pode molecules can be prepared by the reaction of Me₂As? R? OH (R ? CH₂CH₂, CH₂CH₂(OCH₂CH₂)₂) with the amino compounds Me_x(NMe₂)_z (A ? As, Si). These reactions result in the formation of molecules as Me_xA(ORAsMe₂)_z.     

Structural studies on 3-acetyl-1,5-diaryl and 3-cyano-1,5-diaryl formazan chelates with cerium(III), thorium(IV) and uranium(VI)

Summary Solid complexes of 3-acetyl-1,5-diaryl and 3-cyano-1,5-diaryl formazans were prepared and characterized by elemental analysis, IR, NMR, TGA and DTA analyses. Based on these studies, the suggested general formula for the complexes is [M(HL) _m (OH^–) _n or (NO ₃ ^– or Cl^–) _x ·(H₂O) _y or (C₂H₅OH orDMSO) _z , where HL=formazanM=Ce³⁺, Th⁴⁺, and UO ₂ ²⁺ ,m=1–2,n=0–3,x=0–3,y=0–4 andz=0–3. The metal ions are expected to have coordination numbers 6–8.

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Strukturuntersuchungen an 3-Acetyl-1,5-diaryl- und 3-Cyan-1,5-diaryl-formazan-Chelaten mit Cer(III), Thorium(IV) und Uran(VI)

Zusammenfassung Die hergestellten Chelate wurden mittels Elementaranalyse, IR, NMR, TGA und DTA charakterisiert. Darauf basierend wird die generelle Formel [M(HL) _m (OH^–) _n bzw. (NO ₃ ^– oder Cl^–) _x ·(H₂O) _y oder (C₂H₅OH bzw.DMSO) _z ] vorgeschlagen, wobei HL=Formazan,M=Ce³⁺, Th⁴⁺ oder UO ₂ ²⁺ ,m=1–2,n=0–3,x=0–3,y=0–4 undz=0–3. Die Metallionen haben Koordinationszahlen von 6–8.

     

Characterization of metal glycinate complexes by electrospray Q-TOF-MS/MS and their determination by capillary electrophoresis–ICP-MS: application to premix samples

A method was developed for the determination of metal complexes with glycine (glycinates, [M(Gly)_x(H₂O)_y(SO₄)_z]_n, where M denotes Zn, Cu, Mn and Fe) in premix samples used for the preparation of animal feeds enriched in essential trace elements. The method was based on the extraction of the glycinates with 10 mM ammonium acetate (pH 7.4) followed by their determination using capillary electrophoresis with ICP MS detection. The stability of the glycinates in solution was verified by electrospray TOF-MS. Each supplement was shown to be a mixture of complexes, with polymerization degrees ranging from n = 1 to n = 4 (depending on the metal), that were fully or partially dehydrated. The metal glycine complex moiety was found to be preserved during capillary electrophoresis. The detection limits, calculated as three times the standard deviation of the blank plus the blank, were between 0.05 and 0.2 μg mL⁻¹ (as the metal), and the calibration curves were linear, allowing the analysis of premix samples. Repeatability for glycinate standards was below 12%, and analytical precision was typically within 15%.     

Synthesis and Characterization of Some Ru( tmeda ) Complexes Containing Chloride, Hydride, and Vinylidene Ligands

 The polymeric compound [Ru(cod)Cl₂] _x (cod = cyclooctadiene) reacts with 2 equivalents of tmeda (N,N,N′,N′-tetramethylethylenediamine) in refluxing MeOH to afford trans-[Ru(cod)(tmeda)(Cl)(H)] (1), which upon treatment with CHCl₃ is readily converted to the dichloro complex trans-[Ru(cod)(tmeda)Cl₂] (2). When [Ru(cod)Cl₂] _x is reacted with tmeda under an atmosphere of H₂ (3 bar), the bis-tmeda complex trans-[Ru(tmeda)₂Cl₂] (3) is obtained in 80% yield. DFT calculations revealed that 3 is by 52 kJ/mol more stable than the corresponding cis isomer. Attempts to prepare the coordinatively unsaturated complex [Ru(tmeda)₂Cl]⁺ by reacting 1 with TICF₃SO₃ were unsuccessful. According to DFT calculations, however, such a complex should be stable and, interestingly, should adopt a square pyramidal rather than a trigonal bipyramidal structure. If halide abstraction of 3 is performed in the presence of terminal alkynes HC*CR (R*t-Bu, n-Bu), the cationic vinylidene complexes [Ru(tmeda)₂(Cl)(*C*CHR)]⁺ (4a,b) are obtained.     

Structural Studies of New Sulfito Mercurates(II) with General Formula xM[XHgSO3]middot;yHgX2·zMX·nH2O (M = NH4, K; X = Cl,Br)

Several solid phases with the general formula xM[XHgSO₃]·yHgX₂·zMX·nH₂O were obtained from aqueous solutions during phase formation studies in the systems M₂SO₃/HgX₂ (M = NH₄, K; X = Cl, Br). All phases were structurally characterized on the basis of single crystal X‐ray diffraction data and adopt new structure types. Compounds with x, y, z = 1 and n = 0 are isostructural (structure type I ) and crystallise with two formula units in space group P2₁/m and lattice parameters of a ≈ 9.7, b ≈ 6.2, c ≈ 10.4Å, β ≈ 111°. Compounds with x, y = 1 and z, n = 0 (structure type II ) crystallize in space group Cmc2₁ with four formula units and lattice parameters of a ≈ 5.9, b ≈ 22.0, c ≈ 6.9Å. The structures with x = 2, y, z = 1 and n = 0 are likewise isostructural (stucture type III ) and consist of four formula units in space group Pnma with lattice parameters of a ≈ 22.2, b ≈ 6.1, c ≈ 12.4Å. K[HgSO₃Cl]·KCl·H₂O is the only representative where x = 1, y = 0, z = 1 and n = 1 (structure type IV ). It is triclinic (space group ) with four formula units and lattice parameters of a = 6.1571(8), b = 7.1342(9), c = 10.6491(14) Å, α = 76.889(2), β = 88.364(2), γ = 69.758(2)°. Characteristic for all structures types is the segregation of the M⁺ cations and the anions and/or HgX₂ molecules into layers. The [XHgSO₃]⁻ anions are present in all structures and have m symmetry, except for K[HgSO₃Cl]·KCl·H₂O with 1 symmetry (but very close to m symmetry). The different [XHgSO₃] units exhibit very similar Hg‐S distances (average 2.372Å) and are more or less bent with ∠(X‐Hg‐S) angles ranging from 159.7 to 173.7°. The molecular HgX₂ entities present in structure types I ‐ III deviate only slightly from linearity with ∠(X‐Hg‐X) angles ranging from 174 to 179°. The structures are stabilised by interaction of the K⁺ or NH₄⁺ cations that are located between the anionic layers or in the vacancies of the framework, by K‐O contacts or, in case of ammonium compounds, by medium to weak hydrogen bonding interactions of the type N‐H···O.     

Interaction features of cerium (III) and europium (III) acetate and pivalate with monoethanolamine

The composition of mixed-ligand complexes of cerium (III) and europium (III) acetates and pivalates with monoethanolamine (MEA) depends on the synthesis conditions and the nature of carboxylate ligand. We prepared solid complexes [Ln(Piv)₃(MEA) _x ], where Ln = Ce, Eu; HPiv-2,2-dimethylpropionic (pivalic) acid; x = 1, 1.5, and gel-like hydroxocomplexes [Ln(Carb) _{n − x − y} ,(NO₃) _x (OH) _y (MEA) _w (H₂O) _z ], where Ln = Ce, n = 4; Ln = Eu, n = 3; HCarb is acetic acid (HAcet) or HPiv. The values of the coefficients x, y, w, and z depend on the synthesis conditions and heat treatment. Prepared compounds were characterized by IR and ¹H NMR spectroscopies, elemental and thermal analyses, and MALDI-MS. The ESI-MS method was used to characterize the processes occurring in the solutions.     

Synthesis and application of novel fluoroalkyl end-capped cooligomers having adamantane as a pendant group

Fluoroalkyl end-capped cooligomers having adamantane as a pendant group [R_F-(Ad-HAc) _x –(Co-M) _y -R_F] were prepared by the reactions of fluoroalkanoyl peroxide with 3-hydroxy-1-adamantylacrylate (Ad-HAc) and comonomers (Co-M) such as acrylic acid (ACA), N,N-dimethylacrylamide (DMAA), and acryloylmorpholine (ACMO) under mild conditions. Thermogravimetric analyses (TGA) showed that thermal stability of R_F-(Ad-HAc) _x –(Co-M) _y -R_F was superior to that of the corresponding fluoroalkyl end-capped cooligomers having adamantane in the main chains [R_F-(Ad) _x –(Co-M) _y -R_F] and the fluoroalkyl end-capped homooligomers possessing no adamantyl segments [R_F-(M) _n -R_F]. It is interesting to note that fluoroalkyl end-capped Ad-Hac–DMAA cooligomer [R_F-(Ad-HAc) _x –(DMAA) _y -R_F] was found to form the nanometer size-controlled cooligomeric aggregates which consist of around 16 fluorinated cooligomeric molecules in methanol/water mixed solvents. Furthermore, these fluorinated cooligomeric aggregate could occupy around 320 ADMDD [5-(2-adamantylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione] molecules as guest molecules per aggregate core, although ADMDD could not be encapsulated into the R_F-(Ad) _x –(Co-M) _y -R_F cooligomeric and R_F-(M) _n -R_F homooligomeric aggregate cores under similar conditions.     

Investigation into the formation of heteronuclear clusters of formula [{Ru<Subscript>6</Subscript>C(CO)<Subscript>16</Subscript>Ag<Subscript>2</Subscript>X}<Subscript>2</Subscript>]<Superscript>2−</Superscript> (X = Cl,Br or I)

Reaction of [Ru₆C(CO)₁₆]²⁻ with an excess of AgX (X = Cl, Br or I) affords heteronuclear clusters of formula [{Ru₆C(CO)₁₆Ag₂X}₂]²⁻ in 80% yield, which for X = I and X = Br/Cl were crystallographically characterised. The formation of the cluster was followed in solution using electrospray ionisation mass spectrometry (ESI-MS), which revealed the presence of a wide range of clusters with the general formula [{Ru₆C(CO)₁₆} _x Ag _y X _z ]^{(2x−y+z)−} where x = 1 or 2, y = 1, 2, 3 or 4 and z = 0, 1 or 2. The high yield of the product despite the evident complicated solution speciation is attributed to selective crystallisation of the observed compound driving the equilibrium toward this product.     

Integrated spatial electron populations in molecules: Application to simple molecules

The electron projection function P(x, z) = ∫ ρ(x, y, z) dy is used to evaluate charge transfer and covalency in two series of molecules, LiX and CH₃X (X = Li, BeH, BH₂, CH₃, NH₂, OH, and F), with wavefunctions derived from STO-3G, 4-31G, and, in some cases, 6-31* ab initio calculations. The precision of the method and comparison with Mulliken populations analysis are described. Particular attention is given to CH₃Li which by our criteria is wholly ionic.     

Complex Formation of Rhenium (V) with Benzimidazole in Acidic Media

Rhenium(V) complexes of 1H-benzimidazole (L), isolated from acidic media: (HL)₂[ReOX₅]·(H₂O) _n and [ReOL _x X _y (H₂O) _z ](H₂O) _n (HL and L are protonated and deprotonated forms of benzimidazole; X = Cl^-, Br^-) were studied by means of IR spectroscopy, ¹H NMR spectroscopy, and thermal analysis.     

Tetraalkylammonium fluorooxoperoxovanadates

Summary Compounds crystallizing from theMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄, N(C₂H₅)₄, N(C₄H₉)₄) system have been characterized by elemental analysis, vibrational spectra, and X-ray powder patterns. Besides [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) and [N(CH₃)₄]₃[V₂O₂(O₂)₄F] (2) which correspond to the known compoundsM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) and (NH₄)₃[V₂O₂(O₂)₄F]·2H₂O, respectively, complexes of two new types have been obtained: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O(x0.25,3) and the first trinuclear peroxo complex of vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O(4).

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Tetraalkylammonium-Fluorooxoperoxovanadate

Zusammenfassung Aus dem SystemMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄), N(C₂H₅)₄, N(C₄H₉)₄) kristallisierende Verbindungen wurden mittels Elementaranalyse, Schwingungsspektroskopie und Röntgendiffraktion charakterisiert. Neben [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) und [N(CH₃)₄]₃][V₂O₂(O₂)₄F] (2), welche den bekannten VerbindungenM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) und (NH₄)₃[V₂O₂(O₂)₄)F]·2H₂O entsprechen, wurden zwei neue Typen von Komplexen erhalten: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O (x0.25,3) und der erste dreikernige Peroxokomplex von Vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O (4).

     

Synthesis and Characterization of Some Ru(tmeda) Complexes Containing Chloride, Hydride, and Vinylidene Ligands

Summary.  The polymeric compound [Ru(cod)Cl₂] _x (cod = cyclooctadiene) reacts with 2 equivalents of tmeda (N,N,N′,N′-tetramethylethylenediamine) in refluxing MeOH to afford trans-[Ru(cod)(tmeda)(Cl)(H)] (1), which upon treatment with CHCl₃ is readily converted to the dichloro complex trans-[Ru(cod)(tmeda)Cl₂] (2). When [Ru(cod)Cl₂] _x is reacted with tmeda under an atmosphere of H₂ (3 bar), the bis-tmeda complex trans-[Ru(tmeda)₂Cl₂] (3) is obtained in 80% yield. DFT calculations revealed that 3 is by 52 kJ/mol more stable than the corresponding cis isomer. Attempts to prepare the coordinatively unsaturated complex [Ru(tmeda)₂Cl]⁺ by reacting 1 with TICF₃SO₃ were unsuccessful. According to DFT calculations, however, such a complex should be stable and, interestingly, should adopt a square pyramidal rather than a trigonal bipyramidal structure. If halide abstraction of 3 is performed in the presence of terminal alkynes HC*CR (R*t-Bu, n-Bu), the cationic vinylidene complexes [Ru(tmeda)₂(Cl)(*C*CHR)]⁺ (4a,b) are obtained. Received March 26, 2001. Accepted April 26, 2001     

Complexes of (ω-diphenylphosphinoalkyl)diphenylphosphine sulfides with silver nitrate in pyridine

The behavior of the phosphine-phosphine sulfide complexes of silver, [Ph₂P(S)(CH₂) _n PPh₂] _m ·AgNO₃ (n=2 or 4;m=1 or 2), in pyridine was studied. Dissolution of the 1:1 complexes in pyridine leads to destruction of their dimeric structures Ag₂[Ph₂P(S)(CH₂) _n PPh₂]₂(NO₃)₂ (A) to form the complexes Agp_y ⁺−P(Ph₂)(CH₂) _n Ph₂P=S and Agp_y ⁺−S=PPh₂(CH₂) _n PPh₂. The solid complexes isolated from pyridine restore dimeric structure A. According to the data of X-ray diffraction analysis, the 1:2 complex isolated from pyridine has the structure [S=P(Ph₂)(CH₂)₂(Ph₂)P−(NO₃)Ag(Py)−P(Ph₂) (CH₂)₂(Ph₂)P=S]Py. According to the data of IR spectroscopy, dissolution of this complex in chloroform leads to the formation of the dimeric structure Ag₂Ph₂P(S)(CH₂)₂PPh₂]₄(NO₃)₂. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1751–1758, September, 1998.     

Aurophilic interactions in μ‐p‐phenyl­enediethynyl‐bis[(trimethyl phosphite)gold(I)] dichloro­methane hemisolvate

The title compound, [Au₂(C₁₀H₄)(C₃H₉O₃P)₂]·0.5CH₂Cl₂, is a linear monomer in which each Au atom is coordinated by one acetylene and one phosphite group. Molecules are connected through aurophilic interactions, one short and one longer, approximately perpendicular to the intramolecular di(gold acetylide) unit, with an Au⋯Au(x, 1 − y, + z) distance of 3.1733 (2) Å and an Au⋯Au(−x, y, − z) distance of 3.5995 (3) Å. Comparison with related compounds exhibiting aurophilic interactions shows that the packing architecture is not determined by steric factors alone.     

A Selective Conversion of Benzylic Alcohols to the Corresponding Carbonyl Compounds by Means of an Ag(III) Complex

 Carbonyl compounds of the type XPhCOR (R = H, Me, Ph; X = H, Me, Cl, Br) are prepared in high yields by reaction of the corresponding benzylic alcohols XPhCHOHR with KNa₄ [Ag(HIO₆)₂]×12H₂O in alkaline solution. This method allows the selective oxidation of benzylic alcohols in compounds containing other types of alcoholic functional groups.     

Structure of complex salts [Co(NH3)6][Rh(NO2)6] and [Co(NH3)6][(NO2)3Rh(μ-NO2)1+x(μ-OH)2?xRh(NO2)3]·(2-x)(H2O), x = 0.17

The structures of two salts [Co(NH₃)₆][Rh(NO₂)₆] (I) and [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 (II) are solved. Single crystals of the salts are obtained by the counter diffusion method through the gel of aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][Rh(NO₂)₆] is consistent with the diffraction data for a polycrystalline sample of poorly soluble fine salt formed in the exchange reaction between aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 exhibits the stabilizing effect of a large cation in the formation of novel, unknown previously coordination ions: [(NO₂)₃Rh(μ-NO₂)(μ-OH)₂Rh(NO₂)₃]³⁻ and [(NO₂)₃Rh(μ-NO₂)₂(μ-OH)Rh(NO₂)₃]³⁻.