Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)-Komplexe mit verschiedenen 1H-Phosphiren-Liganden,Kristallstrukturen von,und

Synthesis and Spectroscopic Characterization of some Pentacarbonyltungsten(0) Complexes with Various 1H-Phosphirene Ligands: Crystal Structures of , and The tungsten(0) complex 1 reacts upon heating with acetylene derivatives 2a–f in toluene to form benzonitrile and the complexes 4a–f ( 4a : R¹ ? Ph, R² ? H; 4b : R¹ ? Ph, R² ? CH₃; 4c : R¹ ? OEt, R² ? H; 4d : R¹ ? Ph, R² ? CO₂Et; 4e : R¹, R² ? CO₂Me; 4f : R¹, R² ? SiMe₃), which have been isolated by chromatography. Spectroscopic and mass spectrometric data are discussed. The crystal structures of the compounds 4a, b and d were determined by X-ray single crystal structure analysis ( 4a : space group P2₁/n, Z = 4, a = 937,5(2) pm, b = 2202,4(6) pm, c = 1266,3(4) pm, β = 108,94(4)°; 4b : space group P2₁/c, Z = 4, a = 1293,9(2) pm, b = 923,5(1) pm, c = 2223,4(3) pm, β = 92,385(6)°; 4d : space group P2₁/c, Z = 4, a = 955,2(2) pm, b = 3190,9(4) pm, c = 930,7(2) pm, β = 99,64(1)°).     

Methylbis(thiomethanolato)bismut(III) — Synthese,Charakterisierung und mikrobiologische Aktivität

The reaction of methyldibromobismuth(III),MeBiBr₂, with two equivalents of lithium thiomethanolate affords the new dithiolate complexMeBi(SMe)₂ (1). This compound is interesting in terms of its strong biological activity.¹H NMR and mass spectra of1 are discussed. As1 did not show characteristic metastable transitions in the MS under test conditions, ion genesis could partially be proved by using the isotopic labelled derivativeMe*Bi(SMe)₂ (1*) (Me*=¹³CH₃).

     

Anorganische Bi(cyclopentasilanyle): Synthese und spektroskopische Charakterisierung

Inorganic Bi(cyclopentasilanyls): Synthesis and Spectroscopic Characterization Nonachloro- or nonabromocyclopentasilane, which are accessible from nonaphenylcyclopentasilane with HX/AlX₃ (X = Cl, Br), easily can be converted to the bicyclic oligosilanes bi(nonachlorocyclopentasilanyl) ( 7 ) and bi(nonabromocyclopentasilanyl) ( 8 ) upon treatment with (t-bu)₂Hg. The phenylderivative bi(nonaphenylcyclopentasilanyl) ( 6 ) can be synthesized from bromononaphenylcyclopentasilane with naphthyllithium. The reaction of 6 with HX/AlX₃ again affords 7 or 8 . When 7 or 8 are reacted with LiAlH₄, about 15% of cyclopentasilane are obtained along with the expected product bi(cyclopentasilanyl), what demonstrates the remarkable sensitivity of the central Si? Si-bond in 7 and 8 towards nucleophilic attack. A smaller binding energy of the central Si? Si-bond in 7 and 9 , however, cannot be deduced from mass spectroscopic studies.     

Synthese und spektroskopische Eigenschaften neuer komplexierter Triphosphane

Synthesis and Spectroscopy of new Triphosphine Complexes The reaction of PCl₃ with [HPPh₂W(CO)₅] in the presence of NEt₃ affords stepwise the diand triphosphine complexes [Cl₂PPPh₂W(CO)₅] and ClP[PPh₂W(CO)₅]. Triphosphine complexes of the type [{M′(CO)₅}(H)P{PPh₂M(CO)₅}] (M = M′ = Cr or Mo) are not formed from the reaction of HP[PPh₂M(CO)₅] with [M′(CO)₅thf]. However they were prepared by reaction of [M′(CO)₅PCl₃] with Li[PPh₂M(CO)₅]. The products were characterized by NMR, IR spectroscopy, and mass spectrometry.     

Synthese,Charakterisierung und Kristallstrukturen von Tetraiodoferraten(III)

Preparation, Characterization, and Crystal Structures of Tetraiodoferrates(III) The extremely air and moisture sensitive tetraiodoferrates MFeI₄ with M = K, Rb and Cs have been synthesized by reaction of Fe, MI and I₂ at 300°C in closed quartz ampoules. The essentially more stable alkylammonium tetraiodoferrates NR₄FeI₄ with R = H, C₂H₅, n-C₃H₇, n-C₄H₉ and n-C₅H₁₁ can be obtained by reaction of Fe, NR₄I and I₂ in nitromethane. The Raman and UV/Vis-spectra of the black compounds show the existence of tetrahedral [FeI₄]^? ions in the structures. The crystal structure of the monoclinic CsFeI₄ (CsTlI₄ type, spgr P2₁/c; a = 7.281(1) Å; b = 17.960(3) Å; c = 8.248(2) Å; β = 107.35(15)°) is built up by tetrahedral [FeI₄]^? ions and CsI₁₁ polyhedra. The crystal structure of the orthorhombic (n-C₅H₁₁)₄NFeI₄ (spgr Pnna; a = 20.143(4) Å; b = 12.683(3) Å; c = 12.577(3) Å) contains tetrahedral [(n-C₅H₁₁)₄N]⁺ ions and [FeI₄]^? ions, respectively.     

Darstellung und spektroskopische Charakterisierung von Di(acido)phthalocyaninatorhodaten(III)

Preparation and Spectroscopical Characterization of Di(acido)phthalocyaninatorhodates(III) Triethylendiaminorhodiumiodide reacts quickly and completely with boiling phthalodinitrile precipitating ?rhodiumphthalocyanine”?, which is purified and dissolved in alkaline media as di(hydroxo)phthalocyaninatorhodate(III). Acidification in the presence of halides or pseudohalides yields less soluble acidophthalocyaninatorhodium reacting with tetra-n-butyl-ammonium(pseudo)halide to give (blue)green tetra-n-butyl-ammoniumdi(acido)phthalocyaninatorhodate(III), (ⁿBu₄N)[Rh(X)₂Pc^2?] (X = Cl, Br, I, N₃, CN, NCO, SCN, SeCN). The asym. Rh? X-stretching vibration (v_as(RhX)) is observed in the f.i.r. at 290 (X = Cl), 233 (Br), 205 (I), 366 (N₃), 347 (CN), 351 (NCO), 257 (SCN) and 214 cm^?1 (SeCN). v_s(RhI) is the only sym. Rh? X-stretching vibration excited at 131 cm^?1 in the Raman spectrum. The m.i.r. and resonance Raman spectra are typical for hexacoordinated phthalocyaninatometalates(III). The influence of the axial ligands is very small. The frequency of the stretching vibrations of the pseudohalo-ligands are as expected (in the case of the ambident ligands the bonding atom is named first): v_as(NN) at 2006 and v_s(NN) at 1270 cm^?1 (N₃); v_as(CN) at 2126 (CN), 2153 (NCO), 2110 (SCN) and 2116 cm^?1 (SeCN). The characteristic π–π*-transitions of the Pc^2?-ligand dominate the UV-vis spectra. The splitting of the Q and N region is discussed and the weak absorbance at ca. 22 kK is assigned to a n–π*-transition.     

Darstellung,Isolierung und Charakterisierung gemischter Thiocyanato(ethylendiamin)rhodium(III)-Komplexe

Preparation, Isolation, and Characterization of Mixed Thiocyanato(ethylenediamine)rhodium(III) Complexes The complexes Na[Rh(SCN)₄(en)] and trans-[Rh(SCN)₂(en)₂]SCN are prepared for the first time. They are isolated from the mixture by column chromatography on aluminia and characterized by the spectra and the CHN analysis.     

Synthese und Charakterisierung neuer Acetylenkomplexe des Mangans und Rheniums

The reaction of the photochemically-generated tetrahydrofuran complexes Cp′(CO)₂M(thf) (Cp′  η⁵-C₅H₅, η⁵-C₅H₄Me, η⁵-C₅Me₅; M  Mn, Re) with various alkynes R¹C₂R² (R¹, R²  H, Me, Ph) yields are acetylene complexes Cp′(CO)₂MR¹C₂R². These compounds were identified from their IR, ¹H NMR, ¹³C NMR and mas spectra.     

Synthese und NMR-spektroskopische Charakterisierung neuer Adenin- und 6-Thioxopurincarboxamidine

Synthesis and NMR-Spectroscopic Characterization of New Adenine- and 6-Thioxopurinecarboxamidines Adenine (1) or 1H-purine-6(7H)-thione ( 4 ) react with carboximidoyl chlorides 2 to yield the adenine-9-carboxamidines 3 or the 6,7-dihydro-6-thioxo-1H-purine-7-carboxamidines 5 and 6,9-dihydro-6-thioxo-1H-purine-9-carboxamidine 6 a , respectively. The structures of the compounds were determined by ¹H- and ¹³C-NMR spectroscopy.     

Darstellung,Isolierung und Charakterisierung Gemischter Cyanatoäthylendiamin-Chrom(III)-Komplexe

Preparation, Isolation, and Characterization of Mixed Cyanatoethylenediamine Chromium(III) Complexes The cyanatoethylenediamine chromates(III) are prepared for the first time. The complexes are characterized by the spectra, the chromium content, and CHN analysis.     

Darstellung,Isolierung und Charakterisierung gemischter Thiocyanato(1,3-diaminopropan)chrom(III)-Komplexe

Preparation, Isolation, and Characterization of Mixed Thiocyanato(1.3-diaminopropane) -chromium(III) Complexes The complexes [Cr(NCS)₄dap]^? and trans-[Cr(NCS)₂(dap)₂]⁺ (dap = 1.3-diaminopropane) are prepared for the first time, isolated as salts and characterized by CHN analysis, chromium contents, the electrophoretic behaviour in dimethylformamide, and by UV, VIS, and IR spectra.     

Darstellung,Isolierung und Charakterisierung gemischter Selenocyanatoäthylendiamin-Chrom(III)-Komplexe

Preparation, Isolation, and Characterization of Mixed Selenocyanatoethylenediamine Chromium(III) Complexes cis-[Cr(NCSe)₄(en)]^? and cis-[Cr(NCSe)₂(en)₂]⁺ are prepared for the first time. They are separated by column chromatography on alumina and characterized by the chromium content and the spectra.     

Darstellung,Isolierung und Charakterisierung Gemischter Cyanothiocyanatoäthylendiamin-Chrom(III)-Komplexe

Preparation, Isolation and Characterisation of Mixed Cyanothiocyanato-ethylenediamine-Chromium(III) Complexes The complex salts K[Cr(CN)(NCS)₃(en)] and [Cr(CN)(NCS)(en)₂]SCN are prepared for the first time. After the preparative isolation by column chromatography on alumima, they are characterized by the chromium content and the spectra.     

Synthese und Charakterisierung neuer Cyclischer und acyclischer Silachalkogenane mit Disilanyleinheiten

Synthesis and Characterization of New Cyclic and Acyclic Silachalcogenanes with Disilanyl Units Synthesis and properties of (4-CH₃? C₆H₄)₃SiSiH₃, (C₆H₅)₂HSiSiH₂C₆H₅, C₆H₅Cl₂SiSiH₃, (C₆H₅)₂ClSiSiH₃, (H₃SiSiH₂)₂Se, H₃SiSiH₂ESiH₃, , as well as characterisation by IR-, MS-, NMR-spectroscopy are described. Reactions of phenylsubstituted disilanes with HCl in the presence of catalytic amounts of AlCl₃ provide chorinated chlorophenylsubstituted disilanes. Condensation of these chlorodisilanes with disilathiane or disilaselenane yield cyclic and acyclic silachalkogenanes containing disilanyl units. The structure of (C₆H₅)₃SiSiH₃ has been determined by X-ray analysis. The compound crystallizes in space group C2/c with the cell dimensions a = 16.366(2), b = 11.458(1), c = 19.719(2) Å, β = 110.93(1)°.     

Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.     

Über die Synthese und spektroskopische Charakterisierung von Strontium‐ und Bariumtetrabromoferrat(III) und die Kristallstruktur von Ba(FeBr4)2

Preparation and Spectroscopic Characterization of Strontium and Barium Tetrabromoferrate(III) and the Crystal Structure of Ba(FeBr₄)₂ The synthesis of the hitherto unknown bromoferrates(III) of alkaline‐earth metals was carried out by heating mixtures of the metals or the binary bromides together with bromine at temperatures of 450 °C and pressures of up to 1500 bar in closed quartz ampoules. The attempts have been successful only with the larger cations of Sr and Ba. In the case of Be, Mg, and Ca only mixtures of the binary bromides with FeBr₃ could be received. By analysis of the Raman and electronic spectra the dark red compounds of Sr and Ba have been characterized as ternary tetrabromoferrates(III) containing tetrahedral FeBr₄ anions. The composition M(FeBr₄)₂ (M = Sr, Ba) has been determined by potentiometric and titrimetric analysis and thermal degradation by thermogravimetry. A single crystal structure determination of Ba(FeBr₄)₂ confirmed the spectroscopic assignments. The orthorhombic crystal structure (space group Pbca; a = 13.054(3) Å; b = 11.093(2) Å; c = 21.764(4) Å; Z = 8) consists of FeBr₄ and BaBr₉ polyhedra.     

Darstellung und spektroskopische Charakterisierung von Fluoro-Chloro-Iridaten(V)

Preparation and Spectroscopic Characterization of Fluoro-Chloro-Iridates(V) By careful oxidation of the pure fluoro-chloro iridates(IV) with BrF₃ in dichloromethane the corresponding pentavalent complexes [IrF₅Cl]^?, cis-[IrF₄Cl₂]^?, and fac-[IrF₃Cl₃]^? are formed without replacements of Cl ligands. The vibrational spectra of these mixed ligand complexes are assigned according to point groups C_4v, C_2v, and C_3v. The increased bond strength compared with the corresponding Ir^IV compounds is indicated by a significant shift to higher energy by about 5–15%. The anomalous intensities of some of the Raman active fundamentals are attributed to the resonance Raman effect. The electronic absorption spectra are measured on the solid tetraethylammonium salts of the fluoro-chloro iridates(V) at 10 K. The strong bands in the UV/VIS region are assigned to charge transfer transitions from π(t_1u, t_2u) and σ(t_1u) Cl orbitals into the π(t)Ir^V level. The intraconfigurational transitions within the t configuration of Ir^V are split by spin orbit coupling and lowered symmetry, observed in the ranges 3000, 5100–6400, 10900–13000, and 18200 cm^?1. The O? O transitions are deduced from the vibrational fine structure; in some cases they are confirmed by electronic Raman bands. With increasing number of F ligands all absorption bands are shifted systematically to higher energies.     

Synthese,Kristallstruktur und spektroskopische Charakterisierung von Tetraphosphorhexaoxid-monoselenid,P4O6Se

Synthesis, Crystal Structure, and Spectroscopic Characterization of Tetraphosphorus Hexaoxide Monoselenide, P₄O₆Se P₄O₆Se has been synthesized by photochemical reaction between P₄O₆ and elemental selenium in CS₂ in presence of iodine as a catalyst. Single crystals form at purification via sublimation. The compound (m. p. 46°C) crystallizes in the monoclinic space group P2₁/c (no. 14) with a = 1 051.8(2), b = 652.9(1), c = 1 178.6(2) pm, β = 109.29(1)°, Z = 4. Within the limits of experimental error, the molecules exhibit C_3v symmetry. IR, Raman, and ³¹P n.m.r. (solution) spectra of the compound are reported and discussed. The geometry of the Molecule as determined by theoretical methods (SCF level) is in good agreement with the experimental results.     

Synthese,Kristallstruktur und spektroskopische Charakterisierung von Tetraphosphorhexaoxiddiselenid P4O6Se2

Synthesis, Crystal Structure, and Spectroscopic Characterization of Tetraphosphorus Hexaoxide Diselenide P₄O₆Se₂ P₄O₆Se₂ has been prepared by photochemical selenation of P₄O₆ with red selenium in CS₂ in presence of catalytical amounts of iodine. Isolation and single crystal growth were performed by fractional crystallization and subsequent sublimation. The compound crystallizes in the monoclinic space group P2₁/c (Nr. 14) with a = 11.473(2); b = 6.536(1); c = 11.796(2) Å; β = 90.06(1)°; Z = 4; R₁ = 0.030; wR² = 0.073. Within the limits of experimental error, the P₄O₆Se₂ molecules exhibit C_2v symmetry in the crystal. Bond lengths and angles within the molecule as well as the arrangement of the molecules within the crystal are discussed; IR-, Raman-, and ³¹P solution NMR data are reported.     

Darstellung und spektroskopische Charakterisierung von Bindungsisomeren Halogenoselenocyanatoosmaten(IV)

Preparation and Spectroscopic Characterization of Bondisomeric Halogenoselenocyanatoosmates (IV) The new compounds [OsCl₅(NCSe)]^2?, [OsCl₅(SeCN)]^2?, tr.-[OsCl₄(NCSe)(SeCN)]^2?, tr.-[OsCl₄I(NCSe)]^2? and tr.-[OsCl₄I(SeCN)]^2? are prepared from [OsCl₅I]^2? and tr.-[OsCl₄I₂]^2? by oxidative ligand exchange with (SeCN)₂ or by reaction with suspended Pb(SeCN)₂ in CH₂Cl₂ and isolated by ion exchange chromatography on DEAE cellulose. The bondisomers are significantly distinguished by the frequencies of innerligand vibrations: ν_CN(Se), ν_CN(N), ν_CSe(N) > ν_CSe(Se), δ_NCSe >, δ_SeCN. The electronic spectra measured at 10 K on the solid salts exhibit in the region 450–650 nm intensive Se → Os and N → Os charge transfer bands. Essentially weaker intraconfigurational transitions (t) are observed near to 2000 and 1000 nm, splitted by lowered symmetry (C_4v) and spin orbit coupling. Only some of the 0–0-transitions may be assigned by measuring electronic Raman bands with the same frequencies.