Carbonylierung von bis(triphenylphosphin)-platin(II)- und -palladium(II)-komplexen in gegenwart von aminen und α-aminosäureestern

The crystal structure of (C₅H₅)₃Pr·CNC₆H₁₁ was determined from single-crystal X-ray diffraction data. The monoclinic unit cell of dimensions a = 8.298(3), b = 21.66(1), c = 11.943(4) Å, and β = 104.98(3)° contains four molecules in general positions of space group P2₁/c. Each molecule is composed of three C₅H₅ rings in a nearly exact trigonal array, η⁵-bonded to the Pr atom at a distance of 2.53 Å to the centroid of each ring, plus a single CNC₆H₁₁ adduct attached to the Pr atom along the trigonal axis at 2.65 Å. The presence of a CN triple bond in the isonitrile moiety and the nearly linear CNC configuration add credence to the previous proposal that there is a pure donor bond from the isonitrile carbon to the metal atom.     

Die Stromspannungskurven von Zirkonium (IV) und Uran(IV)

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Amperometrische Bestimmung von Vanadium(IV) und Titan(IV)

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Carbonyl(organoelement-IVb-bismutin)übergangsmetall-komplexe : Darstellung und komplexchemisches verhalten von tri-t-butyl-, tris(trimethylgermyl)- und tris(trimethylstannyl)bismutin

BiCl₃ reacts with t-butylmagnesium chloride to form tri-t-butylbismuthine (I). The reaction of triethylbismuthine with trimethylstannane results in the elimination of ethane and formation of tris(trimethylstannyl)bismuthine (III). Hexacarbonyl-chromium, -molybdenum and -tungsten, as well as tetracarbonyl-nickel react with I, tris(trimethylgermyl)bismuthine (II), and III with substitution of one CO-ligand, yielding pentacarbonyltris(trimethylelement-IVb)-bismuthine-chromium, -molybdenum, and -tungsten, and tricarbonyltris(trimethylelement-IVb)bismuthinenickel, respectively. The IR, Raman and ¹H NMR spectra of the new compounds are discussed.     

Darstellung und spektroskopische Charakterisierung von bindungsisomeren Halogenoselenocyanato-Osmaten(IV) und -Rhenaten(IV)

Preparation and Spectroscopic Characterization of Bond Isomeric Halogenoselenocyanato-Osmates(IV) and -Rhenates(IV) By oxidative ligand exchange of appropriate chloro-iodo complexes of Os^IV or Re^IV with (SeCN)₂ in CH₂Cl₂ or by heterogeneous reaction with Pb(SeCN)₂ or AgSeCN in CH₂Cl₂ the new complexes cis-[OsCl₄(NCSe)(SeCN)]^2?, tr.-[OsCl₄Br(NCSe)]^2?, tr.-[OsCl₄Br(SeCN)]^2?, [ReCl₅(NCSe)]^2?, [ReCl₅(SeCN)]^2?, tr.-[ReCl₄I(NCSe)]^2?, tr.?[ReCl₄(NCSe)(SeCN)]^2? and tr.?[ReCl₄(NCSe)₂]^2? are formed and isolated as pure compounds by ion exchange chromatography on DEAE-cellulose. The bond isomers are significantly distinguished by the frequencies of innerligand vibrations: n?_CN(Se) > n?_CN(N); n?_CSe(N) > n?_CSe(Se); δ_NCSe > δ_SeCN. The electronic spectra (10 K) of the solid salts reveal a bathochromic shift for the charge transfer bands of the Se isomers as compared with the corresponding N isomers. The intra-configurational transitions are observed for the Os^IV complexes at 600 to 2400 and for the Re^IV complexes at 500 to 1600 nm. The ⁷⁷Se nmr signals of the Os^IV bond isomers are registrated for Se binding in the region 970 to 1040 ppm, for N coordination downfield at 1540 to 1640 ppm.     

Hydroxoplatinate(IV) von Calcium,Strontium und Barium

Hydroxoplatinates(IV) of Calcium, Strontium, and Barium CaPt(OH)₆, CaPtO₂(OH)₂, SrPt(OH)₆ · 2 H₂O, and BaPt(OH)₆ were prepared by precipitation from alkali hydroxoplatinate(IV) solution with earth alkali salt solutions, and characterized by X-ray diffraction and chemical analysis. The crystal structure of CaPt(OH)₆, space group P3 1c-;D, with isolated octahedral Pt(OH)₆ ions, was determined by X-ray powder data. Probable hydrogen positions are calculated, and hydrogen bonding is discussed.     

Darstellung und Eigenschaften von Blei(IV)-arsenat-Gelen und kristallinem Blei(IV)-hydrogenarsenat-monohydrat

Lead(IV) acetate reacts with aqueous arsenic acid to yield lead(IV) arsenates, the state of which depends on the conditions of precipitation. At room temperature amorphous precipitates or gelatinous masses are obtained. Also clear solutions are obtained, which need sometime to become gelatinous. At 90°C colourless crystalline lead(IV) hydrogenarsenate-monohydrate, Pb(HAsO₄)₂ · H₃O, is obtained, isotypic with lead(IV) hyrdrogen-phosphate-monohydrate.     

Elektrochemische untersuchung von bis(diphenyldithiophosphin) disulfid

The electrochemical behaviour of bis(diphenyldithiophosphine)disulphide (RSSR) and mercuric diphenyldithiophosphinate [(RS)₂Hg] in ethanol-lithium perchlorate and ethanol-sulphuric acid media was studied by the methods of classical polarography, and electrolysis at controlled-potential and at a rotating disc platinum electrode. The data obtained show that RSSR is not reduced directly on the dropping mercury electrode but is adsorbed. It then undergoes a rapid chemical reaction causing the formation of (RS)₂Hg, which is electroactive. The electrolysis at controlled potential proves that (RS)₂Hg undergoes a two-electron reduction, giving diphenyldithiophosphinic acid (RSH) as a main product, whereas the oxidation of RSH leads to the production of (RS)₂Hg. Regardless of the fact that the chemical and adsorption equilibria during reduction of RSSR and (RS)₂Hg are complex, the coulometric generation of RSH is not difficult to achieve, and permits the use of RSSR as a coulometric reagent.     

Trennung und Charakterisierung von Chloro-aquo-hydroxo-oxo-osmaten(IV)

Separation and Characterization of Chloro-aquo-hydroxo-oxo-osmates(IV) As a result of the acidic hydrolysis of hexachloroosmate(IV), OsCl₆^2?, and/or the careful reduction of osmium tetroxide with iron(II) sulfate in hydrochloric acid products have been obtained which have been separated by column chromatography using diethylaminoethyl cellulose. On the basis of the analytically determined Os:Cl ratios, the ionic charges that could be deduced from the elution behaviour, and the absorption spectra the products have been characterized as the monomers OsCl₅(H₂O)^?, cis-OsCl₄(OH)(H₂O)^?, fac-OsCl₃(OH)₂(H₂O)^? and mer-OsCl₃(OH)(H₂O)₂, the O-bridged dimers Cl₅Os? O? OsCl₅^4?, cis-(H₂O)Cl₄Os? O? OsCl₄(H₂O)^2?and fac-(H₂O)(OH)Cl₃Os? O? OsCl₃(OH)(H₂O)^2? and the hydrogen bridges forming OH-bridged dimers shown in “Inhaltsübersicht”.     

Darstellung,Kristallstrukturen und Schwingungsspektren von bindungsisomeren Pentabromorhodanoosmaten(IV)

Synthesis, Crystal Structures and Vibrational Spectra of Linkage Isomeric Pentabromorhodanoosmates(IV) By treatment of (n‐Bu₄N)₂[OsBr₅I] with (SCN)₂ in dichloromethane the linkage isomers (n‐Bu₄N)₂[OsBr₅(NCS)] and (n‐Bu₄N)₂[OsBr₅(SCN)] are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[OsBr₅(NCS)] (monoclinic, space group P2₁/n, a = 10.955(5), b = 11.649(5), c = 35.478(5) Å, β = 91.92(1)°, Z = 4) and (CH₂Py₂)[OsBr₅(SCN)] (monoclinic, space group P2₁/n, a = 12.244(2), b = 10.134(3), c = 15.882(4) Å, β = 107.91(2)°, Z = 4) have been performed. The thiocyanate group is coordinated with the Os–N–C angle of 168° for N bonding and the Os–S–C angle of 110° for S bonding. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra of both linkage isomers are assigned by normal coordinate analysis. The valence force constants are f_d(OsN) = 1,81 and f_d(OsS) = 1,42 mdyn/Å.     

Darstellung,Eigenschaften und Kristallstruktur von Bis(phthalocyaninato)cer(IV)

Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure.     

Difluorophosphate von Zinn(IV) und Antimon(V)

Difluorophosphates of Tin (IV) and Antimony(V) Preparation and properties of SnCl₂(PO₂F₂)₂ (l), Cl₄Sb(O₂PF₂) (2) and F₄Sb(O₂PF₂) (3) are described. According to their vibrational spectra the structures are assumed. ³¹P-nmr spectra of 2 and 3 are given. 1 is characterised additional by its ¹¹⁹Sn-Mössbauer spectrum.     

Zur Bestimmung von Selen(IV), Tellur(IV) und Zinn(IV) als Sulfid

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Die gaschromatographische Trennung von Zinn(IV)- und Titan(IV)-chlorid

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