Hexamethylphosphorsäuretriamid als Ligand, 2. Mitt.: Umsetzungen von [Co(HMPT)4]2+ mit Chlorid-, Bromid- und Jodidionen

Zusammenfassung Folgende Koordinationsformen entstehen aus [Co(HMPT)₄]²⁺ bei Zusatz von Halogenidionen in Hexamethylphosphorsäuretriamid (HMPT): [Co(HMPT)₃Cl]⁺, [Co(HMPT)₂Cl₂], [Co(HMPT)Cl₃]^–, [CoCl₄]^2–, [Co(HMPT)₃Br]⁺, [Co(HMPT)₂Br₂] und [Co(HMPT)₃J]⁺.

---

Hexamethylphosphoric triamide as a ligand II: Reactions of Co(HMPT)₄ ²⁺ with chloride, bromide, and iodide ions

The following coordination species are formed from [Co(HMPT)₄]²⁺, by addition of halide ions in hexamethylphosphoric triamide (HMPT): [Co(HMPT)₃Cl]⁺, [Co(HMPT)₂Cl₂], [Co(HMPT)Cl₃]^–, [CoCl₄]^2–, [Co(HMPT)₃Br]⁺, [Co(HMPT)₂Br₂] and [Co(HMPT)₃J]⁺.

---

---

Mit 7 Abbildungen

---

V. Gutmann, A. Weisz undW. Kerber, 1. Mitt., Mh. Chem.100, 2096 (1969).     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Halogenation of π-cyclopentadienyltricarbonylrhenium and π-cyclopentadienyl(triphenylphosphine)dicarbonylrhenium

Conclusions The following previously unknown rhenium semicoordinaticn compounds were synthesized: [-C₅H₅Re(CO)₂PPh₃Cl]⁺Cl^–, [-C₅H₅Re(CO)₃Cl]⁺Cl^–, [-C₅-H₅Re(CO)₂PPh₃Cl]⁺Be₄, [-C₅H₅Re(CO)Cl₂]⁺ [Re(CO)₄Cl₂]^–, and -C₅H₅Re(CO)₂I₂, the latter of which was separated into the cis and trans isomers.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimlcheskaya, No. 2, pp. 408–413, February, 1981.The authors express their gratitude to V. F. Sizom, P. V. Petrovskii, and B. V. Lokshin for taking the mass, IR, and PMR spectra.     

Initial state and transition state contributions to reactivity in mercury(II)-catalysed aquation of thetrans-[Rh(en)2Cl2]+, [Cr(NH3)5Cl]2+, andcis-[Cr(NH3)4(OH2)Cl]2+ cations in binary aqueous solvent mixtures

Summary Rate constants are reported for mercury(II)-catalysed aquation of thetrans-[Rh(en)₂Cl₂]⁺, [Cr(NH₃)₅Cl]²⁺, andcis-[Cr(NH₃)₄(OH₂)Cl]²⁺ cations in water and in methanol-, ethanol-, and acetonitrile-water solvent mixtures. In the case oftrans-[Rh(en)₂Cl₂]⁺, the dependence of rate constants on mercury(II) concentration indicates reaction through a binuclear (Rh-Cl-Hg bridged) intermediate. The dependence of the equilibrium constant for the formation of this intermediate and of its rate constant for dissociation (loss of HgCl⁺) on solvent composition have been established. With the aid of measured solubilities, published ancillary thermodynamic data, and suitable extrathermodynamic assumptions, the observed reactivity trends for these mercury(II)-catalysed aquations are dissected into initial state and transition state components. The reactivity patterns for these three complexes are compared with those for mercury(II)-catalysed aquation of other chloro-transition metal complexes, particularlycis-[Rh(en)₂Cl₂]⁺, [Co(NH₃)₅Cl]²⁺, and [ReCl₆]^2–.     

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.     

Solvent and chelation effects on the photoreduction of cobalt(III)–amine complexes in aqueous–organic solvent media

The photoreduction of trans-[Co(NH₃)₄Cl₂]⁺, trans-[Co(en)₂Cl₂]⁺, [Co(dien)Cl₃], [Co(trien)Cl₂]⁺, and [Co(tetren)Cl]²⁺, ions has been studied using a low pressure Hg vapour lamp as light source (254 nm) in aqueous–organic solvents [0–30% (v/v) MeOH or 1,4-dioxane]. Quantum yields for Co^II production by redox decomposition have been determined in all the cases, and increase considerably with the increase in concentration of MeOH or 1,4-dioxane in the binary solvent mixtures under investigation. A plot of log(quantum yield) versus the Grunwald–Winstein Parameter, Y, which is a measure of solvent ionizing power, shows that a different blend of general and specific solvent interacts with the solute. This kind of specific solvent interaction on the reactant/excited state has been analysed using multiple regression: viz. Krygowski–Fawcett and Kamlet–Taft equations. Reasons for the difference in reactivity with chelation are also discussed.     

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.     

The crystal and molecular structure of potassium aquapentachloroiridate(III) and the H, C, N NMR coordination shifts in iridium(III) chloride complexes with 2,2′-bipyridine or 1,10-phenanthroline

The crystal and molecular structure of potassium aquapentachloroiridate(III) (K₂[Ir(H₂O)Cl₅]) was reported. The [Ir(H₂O)Cl₅]²⁻ anions are nearly octahedral, the axial Ir–Cl bond (2.322(2) Å) being shorter than the equatorial ones (2.346(2)–2.360(2) Å); the Ir–O bond length is 2.090(4) Å. Ir(III) chloride complexes with 2,2′-bipyridine (LL = bpy) or 1,10-phenanthroline (LL = phen), of the general formulae K[Ir(LL)Cl₄] and cis-[Ir(LL)₂Cl₂]Cl, were studied by far-IR and ¹H–¹³C, ¹H–¹⁵N HMBC/HMQC/HSQC–NMR. High-frequency ¹H NMR coordination shifts (Δ^1H_coord = δ^1H_complex − δ^1H_ligand; max. ca. +1 ppm) were noted for [Ir(LL)Cl₄]⁻ anions, while for cis-[Ir(LL)₂Cl₂]⁺ cations they had variable sign and magnitude (max. ca. ±1 ppm); they were dependent on the proton position, being mostly expressed for the nitrogen-adjacent hydrogens (H(6) for bpy, H(2) for phen). ¹³C NMR signals were high-frequency shifted (by max. ca. 8 ppm), whereas all ¹⁵N nuclei were shifted to the lower frequency (by ca. 105–120 ppm). The experimental ¹H, ¹³C, ¹⁵N NMR chemical shifts were reproduced by semi-empirical quantum-chemical calculations (B3LYP/LanL2DZ+6-31G^**//B3LYP/LanL2DZ+6-31G*).     

Kinetics of substitution reactions of transition metal complexes in 1,3-dioxolan-2-one + water and 4-methyl-1,3-dioxolan-2-one + water solvent mixtures

Summary Rate constants are reported and discussed for several substitutions of inorganic complexes in ethylene carbonate (1,3-dioxolan-2-one) + water and in propylene carbonate (4-methyl-1,3-dioxolan-2-one) + water solvent mixtures. The reactions include aquation ofcis- and oftrans-[Co(en)₂Cl₂]⁺, aquation oftrans-[Cr(OH₂)₄Cl₂]⁺, bromide substitution at [Pd(Et₄dien)Cl]⁺, thiourea substitution atcis-[Pt(4-NCpy)₂Cl₂], and aquation and cyanide attack at [Fe(X-phen)₃]²⁺ cations.     

X-ray structural analysis of a novel organic metal (BEDT-TTF)4[Hg2Cl6]·PhCl

X-ray structural analysis has revealed that reaction of (BEDT-TTF)[HgCl₃]^– with PhCl leads to the formation of a cation-radical salt (BEDT-TTF)₄[Hg₂Cl₆]· PhCl, which exhibits a laminar crystal structure. The cationic layer is characterized by a grid or lattice network of contracted S...S intermolecular distances (3.396(4)–3.647(5) Å), which unite the BEDT-TTF cations in ribbons or bands, parallel to the [014] direction, and which also bind the ribbons together in a direction close to the [010] axis. The presence of this type of lattice network explains the metallic nature of the conductivity of this salt (BEDT-TTF)₄Hg₂Cl₆]·PhCl in the temperature range 300.0–1.5 K, and is the basis of assigning this salt to a new class of organic, two-dimensional conductors. The [Hg₂Cl₆]^2– anions and PhCl solvent molecules are united via secondary Hg...Cl 3.176(5) Å and Cl...Cl 3.480(6) Å interaction forces to form centrosymmetric tetramers [Hg₂Cl₆PhCl]₂ ^4–, stretched out along the [014] axis direction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2062–2070, September, 1991.The authors wish to acknowledge R. N. Lyubovskaya for supplying the crystals and for helpful discussion of the results.     

Kinetics and mechanism of formation of tetrachloropalladate(II) in the reactions of bis(oxalato)- and bis(malonato) palladate(II) with chloride in acid media

Summary Kinetics of formation of [PdCl₄]^2– from [Pd(ox)₂]^2– and [Pd(mal)₂]^2– has been studies in aqueous acid media in the presence of an excess of chloride ion by stopped-flow spectrophotometry. Both the complexes undergo the transformation in two well separated consecutive steps. In 0.02–0.05 M acid with 0.2 M Cl^–, Pd(AA)^2– dissociates leading to the formation of [Pd(AA)Cl₂]^2– (where AA =ox^2– or mal^2–), which in 0.1–0.6 M acid and 1 M Cl^– forms [PdCl₄]^2– in a relatively slow step. For both steps k_abs=k₀+k₂[H⁺][Cl^–]. Activation parameters corresponding to k₀ and k₂ have been determined. Results indicate that [Pd(mal)₂]^2– is much more labile to substitution than [Pd(ox)₂]^2– and for both the lability is far greater than that of [Pd(bigH)₂]²⁺ and [Pt(ox)₂]^2– reported earlier.     

The preparation and characterisation of chromium(III) complexes of C-meso-5, 12-dimethyl-1, 4, 8, 11-tetraazacyclotetradecane (LM). Aquation and base hydrolysis kinetics ofcis- andtrans-[CrLMCl2]+

Summary The reaction of [CrCl₃(DMF)₃] with C-meso-5, 12-dimethyl-1, 4, 8, 11-tetra-azacyclotetradecane(L_M) in DMF gives a mixture ofcis-[CrL_MCl₂]Cl (ca. 90%) andtrans-[CrL_MCl₂]Cl (ca. 10%). These complexes are readily separated, as thecis-isomer is insoluble in warm methanol while thetrans-isomer is soluble. Using the dichlorocomplexes as precursors it has been possible to prepare a range ofcis-[CrL_MX₂]⁺ complexes (X=Br^–, NO ₃ ^– , N ₃ ^– , NCS^– and X₂=bidentate oxalate) and alsotrans-[CrL_MX₂]⁺ complexes (X=Br^–, H₂O or NCS^–). The spectroscopic properties and detailed stereochemistry of the complexes are discussed.The aquation and base hydrolysis kinetics ofcis- andtrans-[CrL_MCl₂]⁺ have been studied at 25° C. Base hydrolysis of thecis-complex is extremely rapid with K_OH =1.46×10⁵ dm³ mol^–1 at 25° C. This unusual reactivity appears to be associated with thetrans II stereochemistry of thesec-NH centres of the macrocycle. Base hydrolysis of thetrans complex with thetrans III chiral nitrogen stereochemistry is quite normal with k_OH =1.1 dm³ mol^–1 s^–1 at 25° C.     

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.     

Electronic structure and molecular properties of the [Mo6X8L6]; X = Cl, Br, I; L = F, Cl, Br, I clusters

Relativistic TDDFT calculations including spin orbit interactions via the ZORA approximation and solvent effects were carried out on the [Mo₆X₈L₆]²⁻ X = Cl, Br, I ; L = F, Cl, Br, I clusters. These calculations indicate that the closely spaced lowest excited states are largely centered on the cubic [Mo₆X₈]⁴⁺ core. Thus, our calculations and the electronic similarities with the strongly luminescent [Mo₆Cl₈Cl₆]²⁻, [Mo₆Br₈Br₆]²⁻ and [Mo₆I₈I₆]²⁻ clusters, suggest that the clusters [Mo₆Cl₈F₆]²⁻, [Mo₆Br₈F₆]²⁻, [Mo₆I₈F₆]²⁻, [Mo₆I₈Cl₆]²⁻ and [Mo₆I₈Br₆]²⁻ studied here might be also luminescent. The calculated bond energies and reactivity indexes indicate that the most labile clusters are those with axial iodide ligands.     

Crystal and molecular structure of organic semiconductor (ET)8[Hg4Cl12] · 2C6H6

A new organic semiconductor, (ET)₈[Hg₄C1₁₂] · 2C6H6, obtained in the ET⁺-HgCl ₃ ^– -PhF system has been studied by X-ray structural analysis. Radical cations of bis(ethylenedithio)tctrathiafulvalene (ET) in the organic layer of the structure are packed in stacks ofa-type. The average angle between the planes of ET cations from adjacent stacks is 50.1°. The anionic layer is formed by four-charge centrosymmetric [Hg₄Cl₁₂]^4– complexes and benzene solvate molecules. A comparative crystal-chemical study of the salts obtained by the reaction in the ET⁺-HgX ₃ ^– -PhY system (where X = Cl, Br, and I; Y = F, Cl, and Br) made it possible to reveal a substantial effect of the sizes of the X and Y atoms on the composition of the salts and on the structural characteristics of the layers, which are responsible for the various conductivities of these salts.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 386–391, February, 1996     

Solubility of dichlorotetraalkylpyridinecobalt III hexachlororhenate(IV) in water + methanol mixtures: Free energies of transfer of the complex cation from water into the mixtures

The solubility of salts [Co(3Rpy)₄Cl₂]₂]ReCl₆] has been determined in water + methanol mixtures. By comparing these with the solubilities of the salt Cs₂ReCl₆ and using calculated activity coefficients for the ions in the water+methanol mixtures, values for {G _t ^o (Co(3Rpy)₄Cl ₂ ⁺ )–G _t ^o (Cs⁺)} can be determined where G _t ^o is the standard Gibbs free energy of transfer from water to an aqueous mixture. G _t ^o (Cs⁺) from the solvent sorting scale and from the TPTB scale are then used to calculate G _t ^o (Co(3Rpy)₄Cl ₂ ⁺ ). These two sets of values for G _t ^o (Co(3Rpy)₄Cl ₂ ⁺ ) on the differing scales are then inserted into a free energy cycle applied to the bond extension Co(3Rpy)₄Cl ₂ ⁺ (initial state)Co(3Rpy)₄Cl²⁺+Cl^– (transition state) for the solvolysis in water and in water + methanol mixtures to produce values for G _t ^o (Co(3Rpy)₄Cl²⁺) using both scales. Data for the solubilites of [Copy₄Cl₂]₂[ReCl₆] and [Co(4Rpy)₄Cl₂]₂[ReCl₆] have been re-calculated to compare free energies of transfer for these complex cations with those specified above.     

Synthesis,radiochromatography and biodistribution of99mTc-dimethylphosphinoethane (DMPE) complexes

The title complexes were prepared from no-carrier-added^99mTc–TcO ₄ ^– and the air-sensitive reducing ligand DMPE under argon in ethanol-water. At acidic pH [Tc(III)Cl₂ dmpe₂]⁺ was formed, while alkaline pH led to the formation of [Tc(I)dmpe₃]⁺. About 150°C and at least 10^–3M DMPE was needed to achieve over 95% yield in less than 1 hour, otherwise the [Tc(V)O₂dmpe₂]⁺ intermediate was present. Electrophoresis demonstrated the unit positive charge and reversed-phase ion-pair HPLC provided separation and identification of^99mTc-products by direct comparison with known⁹⁹Tc-complexes. In rats the^99mTc-complexes were excreted by kidneys and liver and reached high heart/blood but only low heart/lung and heart/liver ratios. In dogs satisfactory myocardial scintigrams were obtained in spite of high liver activity.     

Dialkyltriazaniumsalze, 4. Mitt.: Die Chloraminierung von sekundären aliphatischen Aminen

Zusammenfassung Die Chloraminierung von sekundären aliphatischen Aminen in Gegenwart von NH₃ führt zu 2,2-Dialkyltriazaniumchloriden. Auf diese Weise konnte das schon bekannte 2,2-Dimethyl- und 2,2-Diäthyltriazaniumchlorid sowie die noch unbekannten Verbindungen [(C₃H₇)₂N₃H₄]⁺Cl^–, [(C₄H₉)₂N₃H₄]⁺Cl^– und das 2-Methyl-2-benzyltriazaniumchlorid aus den entsprechenden sekundären Aminen dargestellt werden.

---

Chloramination of secondary aliphatic amines

Chloramination of secondary aliphatic amines in the presence of ammonia yields 2.2-dialkyltriazanium chlorides. The known compounds [me ₂N₃H₄]⁺Cl^– and [et ₂N₃H₄]⁺Cl^– and the hitherto undescribed triazanium chlorides [pr ₂N₃H₄]⁺Cl^–, [bu ₂N₃H₄]⁺Cl^–, and 2-methyl-2-benzyltriazanium chloride have been synthesized by this method.

     

Crystal Structure of Triaqua(1,10-diaza-18-crown-6)chlorobarium Chloride

The crystal structure of triaqua(1,10-diaza-18-crown-6)chlorobarium chloride [Ba(DA18C6)Cl(H₂O)₃]⁺Cl^–(I) is studied by X-ray diffraction analysis: space group Pnma, a= 14.912, b= 13.590, c= 10.456 Å, Z= 4. Structure Iis solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation: R= 0.079 for all 3194 measured independent reflections (CAD-4 diffractometer, MoK ). Crystal Iexists as complex guest–host cations and Cl^–anions connected via interionic hydrogen bonds. The cations and anions are located in the msymmetry plane. The Ba²⁺ion (coordination number 10) is in the cavity of the DA18C6 macrocycle and is coordinated by its six heteroatoms (2N + 4O) and also by the Cl^–anion and two O atoms of two water molecules from one side of the macrocycle and by the O atom of the third water molecule from another side. The DA18C6 ligand in Ihas the conformation of a crown with an approximate D _3d symmetry.     

Thermally induced isomerisation and decomposition of diethylenetriamine complexes of nickel(II) in the solid state

Summary Complexes [NiL₂]X₂·nH₂O (L=diethylenetriamine; n=O when X=CF₃CO₂ or CCl₃CO₂; n=1 when X=Cl or Br, and n=3 when X=0.5SO₄ or 0.5SeO₄) and NiLX₂·nH₂O (n=1 when X=Cl or Br; n=3 when X=0.5SO₄ or 0.5SeO₄) have been synthesised and investigated thermally in the solid state. NiLSO₄ was synthesised pyrolytically in the solid state from [NiL₂]SO₄·[NiL₂]X₂ (X=Cl or Br) undergo exothermic irreversible phase transitions (242–282° C and 207–228° C; H=–11.3 kJ mol^–1 and –1.9 kJ mol^–1 for [NiL₂]Cl₂ and [NiL₂]Br₂, respectively). [NiL₂]-phenomenon (158–185° C; H=2.0 kJ mol^–1). NiLX₂· nH₂O (n=1 or 3) undergo simultaneous deaquation-isomerisation upon heating. All the complexes possess octahedral geometry.