Structure of (BEDT-TTF)-Based Organic Metals with Photochromic Nitroprusside Anion (BEDT-TTF)4M[FeNO(CN)5]2, where M = Na+, K+, NH+4, Tl+, Rb+, and Cs+

The crystal and molecular structures of a family of three-component radical cation salts bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), (BEDT-TTF)₄M[NP]₂, where M = Na⁺, K⁺, NH⁺ ₄, Tl⁺, Rb⁺, and Cs⁺and NP is the nitroprusside anion [FeNO(CN)₅]^2–, are studied by X-ray structure analysis. These salts are isostructural and behave as stable metals down to helium temperatures. Their structures are characterized by radical cation layers of the "-type alternating with layers of complex anions [M⁺(NP^2–)₂]^3–. The conducting radical cation system and photochromic nitroprusside anion in the crystals were shown to affect each other. On the one hand, this changes the geometric parameters of the nitroprusside anion as compared to those of the Na₂[NP] · 2H₂O crystals in the ground state and, on the other hand, makes the geometries of the two crystallographically independent BEDT-TTF molecules with a different number of shortened contacts with the anion different. Based on the data of crystallochemical analysis of the (BEDT-TTF)₄M[FeNO(CN)₅]₂structures, we suggest their possible routes of chemical modification with the purpose of changing their physical properties.     

Synthesis,protonation and substitution behaviour of K3[ReO2(CN)4]

Summary The preparation and characterization of salts of the [ReO₂(CN)₄]^3–, [ReO(OH)(CN)₄]^2–, [ReO(H₂O)(CN)₄]^–, [Re₂O₃(CN)₈]^4– and [ReO(NCS)(CN)₄]^2– species are described. The nature of the protonation reactions of [ReO₂(CN)₄]^3– was established by the successful isolation of these salts.     

New pentafluorothiophenoxo derivatives of tin,lead, antimony,bismuth, gold and platinum

Summary Salts of the anions [SnX₅]^–, [SnX₄Cl, [SnX₃Cl₂]^–, [SnX₃]^–, [PbX₃]^–, [SbX₄]^–, [SbX₃Cl]^–, [SbX₂Cl₂]^–, [BiX₄]^–, [AuCl₂]^–, [AuX₂]^–, [AuXCl]^–, [AuX₄]^–, [Au₂X₆]^2– and [PtX₄]^2–, where X^– = C₆F₅S^–, have been isolated and characterised. The neutral SbX₃ and BiX₃ species, have also been isolated and shown to be pyramidal monomers (¹⁹F.n.m.r., i.r., and Raman spectral evidence). Various physical properties of the complexes prepared, as well as their stereochemistries (where these could be ascertained), are similar to those of the known corresponding halogeno compounds of these elements. These results further demonstrate the pseudo-halide nature of the pentafluorothiophenoxide ion.Author to whom all correspondence should be directed at: Laboratoire de Chimie de Coordination, Uniyersité Louis Pasteur, 67008 Strasbourg, France.     

Thermal and photochemical interaction of octacyanometallates(IV), [M(CN)8]4− (M = Mo or W) in the presence of pyrazine

The interactions between [M(CN)₈]^4– (M = Mo or W) and pyrazine (pz) in the solid state and in aqueous solutions have been analysed. In strongly acidic solutions {pzH⁺, [M(CN)₈]^4–} ion pair formation is observed; the pyrazinium salts (pzH)₂(H₃O)₂[Mo(CN)₈]·0.5pz·3H₂O and (pzH)₂K(H₃O)[W(CN)₈]·H₂O have been isolated. The X-ray crystal structure of the latter, and the spectroscopic properties of both, are described. The [W(CN)₈]^4– anion is approximately square antiprismatic (D_4d), with different H-bond environments around the N atoms. The ligand-field photolysis of [M(CN)₈]^4– in the presence of pyrazine in neutral and alkaline solution results in the formation of tetracyanooxometallates(IV) in equilibrium with pentacyanooxometallates(IV) through the [M(CN)₇(pz)]^3– anions as intermediates. The formation of the [M(CN)₆(pz)₂]^2– ion, postulated in the literature to be the final product of the alkaline photolysis, has definitively been excluded.     

Novel Antimony Complexes: [Ph4Sb]4 +[Sb4I16]4− · 2Me2C=O and [Ph4Sb]3 +[Sb5I18]3−

The [Ph₄Sb]₄ ⁺[Sb₄I₁₆]^4– · 2Me₂C=O and [Ph₄Sb]₃ ⁺[Sb₅I₁₈]^3– complexes were synthesized by reacting tetraphenylstibonium salts Ph₄SbX (X = I, OSO₂C₆H₄Me-4) with antimony triiodide in acetone. According to X-ray diffraction data, their tetra- and pentanuclear anions [Sb₄I₁₆]^4– and [Sb₅I₁₈]^3– have cyclic and linear structure, respectively.     

Synthesis and X-ray crystal structures of Cs2[W(bpy)(CN)6]·2H2O and (AsPh4)2[W(bpy)(CN)6]·3.5H2O

The synthesis, spectral properties and crystal structures of Cs₂[W(bpy)(CN)₆]·2H₂O and (AsPh₄)₂[W(bpy)(CN)₆]·3.5H₂O are described. The anions of both salts show distorted antiprismatic geometry with very similar bond lengths and angles. The structure of the [W(bpy)(CN)₆]^2– anion is independent of the type of cation, in contrast to the octacyanotungstate(IV).     

Chiral Pyrrolidinium Ionic Liquids with (−)-Borneol Fragment in the Cation – Synthesis,Physicochemical Properties and Application in Diels-Alder Reaction

A series of chiral pyrrolidinium salts containing (1 S)-endo-(−)-born-2-yloxymethyl substituent in the structure of the cation and six different anions: chloride, tetrafluoroborate [BF₄]⁻, hexafluorophosphate [PF₆]⁻, trifluoromethanesulfonate [OTf]⁻, bis(trifluoromethylsulfonyl)imide [NTf₂]⁻, bis(pentafluoroethylsulfonyl)imide [NPf₂]⁻ and perfluorobutanesulfonate [C₄FS]⁻ were efficiently prepared and extensively characterized. The enantiomeric purity of them was confirmed by NMR analysis with a chemical shift reagent. All salts were characterized with the specific rotation, the solubility in commonly used solvents, thermal properties, including phase transition temperatures and thermal stability. Salts with [PF₆]⁻, [C₄FS]⁻, [NTf₂]⁻ and [NPf₂]⁻ anions were classified as chiral ionic liquids (CILs). Moreover, salts with [NTf₂]⁻ and [NPf₂]⁻ anions were in the liquid state at room temperature and below. Therefore, density and dynamic viscosity, the surface tension and the contact angle on three different surfaces were also measured for them. Additionally, these chiral ionic liquids were tested as solvents in Diels-Alder reaction.     

Metal complexes of 6-chloropurine

Summary Five Cu(II), Pd(II), Cd(II), Pt(IV), and Au(III) complexes of 6-chloropurine have been obtained. The complexes were characterized by elemental analysis, IR,¹H-NMR and¹³C-NMR spectroscopy. On the basis of these data the structure of the complexes and the coordination of the ligand have been proposed. Thus, the physical and chemical methods supported evidence that in acidic medium, with exception of the Cu(II) complex, 6-chloropurine acts in the monoprotonated form neutralizing the charge of [PdCl₄]^2–, [CdCl₄]^2–, [AuCl₄]^– and [PtCl₆]^2– anions. The thermal behaviour of the complexes has also been studied.

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Metallkomplexe von 6-Chlorpurin

Zusammenfassung Es wurden fünf Komplexe von 6-Chlorpurin mit Cu(II), Pd(II), Cd(II), Pt(IV) und Au(III) erhalten. Die Komplexe wurden mittels Elementaranalysen, IR,¹H-NMR und¹³C-NMR charakterisiert. Auf der Basis dieser Daten wurde eine Komplexstruktur und eine bestimmte Koordination der Liganden vorgeschlagen. Physikalische und chemische Methoden beweisen, daß im sauren Bereich [mit der Ausnahme von Cu(II)] das 6-Chlorpurin in der monoprotonierten Form koordiniert, wobei die Ladung von [PdCl₄]^2–, [CdCl₄]^2–, [AuCl₄]^– und [PtCl₆]^2– jeweils neutralisiert wird. Das thermische Verhalten der Komplexe wurde ebenfalls untersucht.

     

Synthesis of nonequilibrium Ir<Subscript>x</Subscript>Re<Subscript>1-x</Subscript> solid solutions. Crystal structure of [Ir(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl]<Subscript>2</Subscript>[ReCl<Subscript>6</Subscript>]Cl<Subscript>2</Subscript>

Synthesis of five binary complex salts with an [Ir(NH₃)₅Cl]²⁺ complex cation is described. The counterions are [ReCl₆]^2–, [IrCl₆]^2–, [ReBr₆]^2–, and Cl^–. A polycrystal X-ray diffraction study has been performed for [Ir(NH₃)₅Cl]₂[ReCl₆]Cl₂, and its crystal structure has been determined. A series of Ir _x Re_1–x phases (0.5 x > 1) were obtained by reductive thermolysis. For the Ir-Re system, the history of the V/Z(x) dependence has been refined.Original Russian Text Copyright © 2004 by S. A. Gromilov, S. V. Korenev, I. V. Korolkov, K. V. Yusenko, and I. A. BaidinaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 508–515, May–June 2004.     

Spatial structure and thermodynamic aspects of Dy(III) complex formation with some mono- and dicarboxylic acids

Spatial structures of complexes [DyAc]²⁺, [DyBz]²⁺, [DyAc₂]⁺ and [DyBz₂]⁺ in aqueous solutions (Ac^– and Bz^–, acetate and benzoate anions, respectively) are studied using the paramagnetic double refraction method. The polyhedra of [DyAc(H₂O)₆]²⁺ and [DyBz(H₂O)₆]²⁺ are dodecahedra with ligands coordinated at one of the edges. In the complexes [DyAc₂(H₂O)₄]⁺ and [DyBz₂(H₂O)₄]⁺ the ligands are coordinated at the edges of a square antiprism at an angle of 50 (55)° to the local symmetry axis of higher symmetry.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1038–1040, June, 1993.     

Halogen-und Pseudohalogenkomplexe von Kobalt(II) in Nitromethan

Zusammenfassung Die neutralen Halogenide und Pseudohalogenide von Kobalt(II) sind in Nitromethan kaum dissoziiert. Bei Zusatz entsprechender Anionen zu Kobalt(II)-perchloratlösungen werden in Nitromethan folgende Koordinationsformen leicht gebildet: CoCl₂, CoCl₃ ^–, CoCl₄ ^2–, CoBr₂, CoBr₃ ^–, CoBr₄ ^2–, CoJ₂, CoJ₃ ^–, CoJ₄ ^2–, Co[N₃]₂, [Co(N₃)₄]^2–, Co[NCS]₂, [Co(NCS)₄]^2–, Co[CN]₂ [Co(CN)₄]^2– und [Co(CN)₅]^3–.

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The neutral halides and pseudohalides of cobalt(II) are nearly undissociated in nitromethane. On addition of the appropriate anion to a solution of cobalt(II)-perchlorate in nitromethane the following coordination forms are easily produced: CoCl₂, CoCl₃ ^–, CoCl₄ ^2–, CoBr₂, CoBr₃ ^–, CoBr₄ ^2–, CoJ₂, CoJ₃ ^–, CoJ₄ ^2–, Co[N₃]₂, [Co(N₃)₄]^2–, Co[NCS]₂, [Co(NCS)₄]^2–, Co[CN]₂, [Co(CN)₄]^2– and [Co(CN)₅]^3–.

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Mit 10 Abbildungen     

Azido-, Rhodano-, Cyano- und Fluorokomplexe des Fe(III)-Ions in Dimethylsulfoxid

Zusammenfassung Auf Grund spektrophotometrischer und konduktometrischer Messungen wurden folgende Koordinationsformen des Eisen(III)-ions mit Azid-, Rhodanid-, Cyanid- und Fluoridionen in Dimethylsulfoxid festgestellt: [Fe(N₃)₄]^–, [Fe(SCN)₆]^3–, [Fe(CN)₂]⁺, Fe(CN)₃, [Fe(CN)₄]^–, [FeF₂]⁺, [FeF₄]^–.

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By means of spectrophotometric and conductometric measurements the following coordination forms of iron(III) with azide-, thiocyanate-, cyanide- and fluoride ions were found in dimethyl sulfoxide: [Fe(N₃)₄]^–, [Fe(SCN)₆]^3–, [Fe(CN)₂]⁺, Fe(CN)₃, [Fe(CN)₄]^–, [FeF₂]⁺, [FeF₄]^–.

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Mit 4 Abbildungen     

Negative ion chemical ionization mass spectrometry of some nitroso compounds with CO2 as reagent gas

Summary Mass spectra of seven N-nitrosamines and five alkyl nitrites, the O-nitroso compounds, have been obtained by low pressure negative chemical ionization with CO₂ as reagent gas. Intense anions were observed at m/z M–32 for N-nitrosamines and at m/z M–30 for alkyl nitrites. Addition products were found at m/z M+12 and M+43 for N-nitrosamines and at m/z M+14 for alkyl nitrites. By using isotopically labeled CO₂, it could be shown that the anions at m/z M+12, M+14 and M+43 correspond to [M - H₂NO + CO₂ ^–, [M – NO + CO₂]^–, and [M – H + CO₂]^–, respectively.

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Negativionen-CI-Massenspektrometrie einiger Nitrosoverbindungen mit CO₂ als Reagensgas

Zusammenfassung Die Massenspektren von sieben N-Nitrosaminen und fünf Alkylnitriten (O-Nitrosoverbindungen) wurden durch negative chemische Ionisation bei niederem Druck mit CO₂ als Reagensgas erhalten. Intensive Anionen wurden bei m/z M–32 für N-Nitrosamine und bei m/z M–30 für Alkylnitrite beobachtet. Additionsprodukte fanden sich bei m/z M+12 und M+43 für N-Nitrosamine sowie bei m/z M+14 für Alkylnitrite. Mit Hilfe von Isotopen-markiertem CO₂ konnte gezeigt werden, daß die Anionen bei m/z M+12, M+14 und M+43, [M – H₂NO + CO₂]^–, [M – NO + CO₂]^– bzw. [M – H + CO₂]^– entsprechen.

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A full account of this work including the negative chemical ionization mass spectra obtained with other reagent gases will be submitted to the Journal of Mass Spectrometry.     

Electronic Structure of the Isolated [CuX6]4– Anions in (AguH2)2[CuX6] (X = Cl,Br; Agu is Aminoguanidine) and CuF2

The electronic structures of the isolated [CuX₆]^4– complex anions (X = F, Cl, Br) were studied by the density functional theory and Hartree–Fock methods. The donor–acceptor interactions in similar anions were shown to be accompanied by the formation of square-planar [CuX₄]^2– complexes, and additional axial ligands were coordinated only through ionic bonds.     

1, 2-Dithiolium salts

A new method for the synthesis of 1, 2-dithiolium hydrogen sulfates by the oxidation of 1, 2-dithiole-3-thiones with hydrogen peroxide in acetic acid has been developed. From 4-(p-tolyl) 1, 2-dithiolium hydrogen sulfate a series of salts containing anions of inorganic, heteroorganic, and organic acids (Cl^–, Br^–, I^–, ClO ₄ ^– , CNS^–, VO ₃ ^– , HMoOO ₄ ^– , S₂O ₃ ^2– , S₂O ₈ ^2– , Cr₂O ₇ ^2– , Fe(CN) ₆ ^3– , Fe(CN) ₆ ^4– , B(C₆H₅) ₄ ^– , F₃CCOO^–, C₆H₂(NO₂)₃O^–) has been obtained. 4-(p-tolyl)-1, 2-dithiolium salts containing the anions NO ₂ ^– , NO ₃ ^– , ClO ₃ ^– , BrO ₃ ^– , SO ₃ ^2– , SO ₄ ^2– , S₂O ₅ ^2– and Cl₃CCOO^– dissolve in water and do not precipitate in double decomposition reactions. The reactions of 4-(p-tolyl)-1, 2-dithiolium hydrogen sulfate with sodium sulfite, disulfide, and hydrogen sulfide lead to the formation of bis[4-(p-tolyl)-1, 2-dithiol-3-yl] sulfide and disulfide and the sodium salt of 4-(p-tolyl-1, 2-dithiole-3-thiol, respectively. The reaction of 4-(p-tolyl)-1, 2-dithiolium hydrogen sulfate with solutions of salts of the alkali metals containing the anions of weak acids F^–, CNO^–, HCO ₃ ^– , CO ₃ ^2– , B₄O ₇ ^2– , HAsO ₄ ^2– , PO ₄ ^3– , CH₃COO^–, ClCH₂COO^–, etc.) forms bis[4-(p-tolyl)-1, 2-dithlol-3-yl] oxide. [8, Table 3].For part I, see [1].     

Mixed Ruthenium–Iridium Carbonyl Cluster Complexes. Synthesis of the Anions [Ru3Ir2(CO)14]2− and [Ru3Ir2(CO)14H]− and Crystal Structures of Their [tetraphenylphosphonium]+ Salts

The reaction of Ru₃(CO)₁₂ and [Ir(CO)₄]^- (as [PPh₄]⁺ or [N(PPh₃)₂]⁺ salts) yields the anion [Ru₃Ir₂(CO)₁₄]^2- (1) which has been found to derive from the intermediate [Ru₃Ir(CO)₁₃]^- anion. Treatment of (1) with acids gives the conjugated hydrido species [Ru₃Ir₂(CO)₁₄H]^- (2). The two anions were characterized by single-crystal X-ray diffraction of their [PPh₄]⁺ salts. [PPh₄]₂[Ru₃Ir₂(CO)₁₄]: space group C2/c, Z=4, a=22.121(5) Å, b=10.546(5) Å, c=25.931(5) Å, =103.870(5)°, R=0.052 and R_w=0.130 for 3128 independent reflections with I>2(I ). [PPh₄][Ru₃Ir₂(CO)₁₄H]: space group P2₁/c, Z=8, a=22.833(5) Å, b=13.893(5) Å, c=25.810(5) Å, =92.650(5)°, R=0.070 and R_w=0.150 for 12141 independent reflections with I>2(I). Both anions 1 and 2 have a trigonal bipyramidal metal frame. There are two independent anions in the asymmetric unit of 2 differing in their ligand stereochemistry.     

Cobalt(II) complexes of 1,2-(diimino-4′-antipyrinyl)ethane and 4-N-(4′-antipyrylmethylidene)aminoantipyrine

Cobalt(II) complexes of the Schiff bases 1,2-(diimino-4-antipyrinyl)ethane (GA) and 4-N-(4-antipyrylmethylidene)aminoantipyrine (AA) have been prepared and characterised by elemental analysis, electrical conductance in non-aqueous solvents, i.r. and electronic spectra, as well as by magnetic susceptibility measurements. The complexes have the general formulae [Co(GA)X]X (X = ClO^– ₄ or NO₃ ^–), [Co(GA)X₂] (X = Cl^–, Br^– or I^–), [Co(AA)₂]X₂ (X = ClO₄ ^–, NO₃ ^–, Br^– or I^–) and [Co(AA)Cl₂]. GA acts as a neutral tetradentate ligand, coordinating through both carbonyl oxygens and both azomethine nitrogens. In the perchlorate and nitrate complexes of GA one anion is coordinated in a bidentate fashion, whereas in the halide complexes both anions are coordinated to the metal, generating an octahedral geometry around the Co ion. AA acts as a neutral bidentate ligand, coordinating through the carbonyl oxygen derived from the aldehydic moiety and the azomethine nitrogen. Both anions remain ionic in the perchlorate, nitrate, bromide and iodide complexes of AA, whereas both anions are coordinated to the metal ion in the chloride complex, resulting tetrahedral geometry around the Co ion.     

The character of interaction of organometallic derivatives of 4-nitrophenol and 4-nitrothiophenol with anions in different media

Interaction of R _n M-derivatives of 4-nitrophenol and thiophenol (R _n M= PhHG, PPh₃Au, Ph₃Sn, Ph₄Sb) with a set of inorganic and organic anions (Cl^–, Br^–, I^–, CN^–, [PhOCO]^–, [4-NO₂C₆H₄OCO]^–) was studied by IR and electronic spectroscopy in solvents with different polarities and coordinating properties (C₆H₆, CH₂Cl₂, DMSO). The dependence of the character of the interaction with the anions on the nature of the metal atom and heteroatom, the type of anions and the nature of the media was analyzed. Such interaction leads to ion-molecular complexes, and also to dissociation of the X-M bond (X = O, S, M = Au, Hg. Sb) with formation of the (4-NO₂C₆H₄X)^– anion even in weakly polar media. Only in the case of 4-NO₂C₆H₄OSnPh₃ does the reaction stop at the stage of complex formation. In other cases the role of complex formation with anions is less than with neutral coordinating reagents.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1838–1841, July, 1996.     

A novel three-dimensional mixed bridging–ligand complex with an unexpected 1,3-diaminopropane bridge

Reaction of K₃[Fe(CN)₆] with [Cu(tn)₂](ClO₄)₂ (tn=1,3-diaminopropane) leads to a novel mixed cyano and tn bridged three-dimensional (3D) bimetallic assembly (1), in which each [Fe(CN)₆]⁴⁻ anion connects six copper(II) cations via six CN⁻ groups, whereas each copper(II) cation is linked to three [Fe(CN)₆]⁴⁻ ions and two other copper(II) ions through Cu–NC–Fe and Cu–tn–Cu linkages, respectively. Magnetic studies reveal weak antiferromagnetic interactions between the nearest Cu^II (S=1/2) ions through the diamagnetic [Fe(CN)₆]⁴⁻ anion.     

Emission,Emissionslebensdauer und Absorption von [Cr urea6]X3-Einkristallen

Emission and absorption polarization spectra as well as emission lifetimes between room temperature and 5 °K have been measured of [Cr urea₆]X₃ single crystals, where X stands for ClO ₄ ^– , J^–, NO ₃ ^– , Br^–, Cl^–, F^–, and X₃ for JSO ₄ ^3– . The strong temperature dependence of the fluorescence/phosphorescence-ratios, and of the emission lifetimes is discussed. The differences between the spectra as well as the emission lifetimes of the various salts can be attributed to an anion dependent trigonal perturbation.

Die Autoren danken dem Verband der Chemischen Industrie für finanzielle Unterstützung dieser Arbeit.