bluuebunny/crossref_metadata_2025 huggingface dataset:
Zur Reaktion von [ { (CO)5Cr} (Ph2PCl)] mit (Me3Si)2Se. Die Kristallstrukturen von [{ (CO)5CrPh2P}2Se], [ { (CO)5Cr} (Ph2P)2Se] und [{ (CO)4Cr} (Ph2P)2Se] / Reaction of [{(CO)5Cr}(Ph2PCl)] with (Me3Si)2Se. The Crystal Structures of [{(CO)5CrPh2P}2Se], [{(CO)5Cr}(Ph2P)2Se] and [{(CO)4Cr}(Ph2P)2Se]
Authors: Merzweiler Kurt , Kersten Hans-Jörg
Published: March 2015

The reaction of [{(CO)5Cr}(Ph2PCl)] with (Me3Si)2Se in toluene at 298 K leads to the compounds [{(CO)5Ph2P}2Se] (1) and [{(CO)5Cr}(Ph2P)2Se] (2). If the reaction is carried out in ether as solvent at 308 K, [{(CO)4Cr}(Ph2P)2Se] (3) is obtained. The structures of 1, 2 and 3 were determined by single crystal X-ray analysis. 1, 2 and 3 contain the Ph2PSePPh2 ligand, which is coordinated to chromium carbonyl fragments in three different ways. 1 consists of a dinuclear complex in which two {(CO)5Cr} fragments are linked by a Ph2PSePPh2 group. In 2, only one phosphorus atom of the Ph2PSePPh2 ligand is bound to a {(CO)5Cr} unit. In 3, the Ph2PSePPh2 group is coordinated as a chelate ligand to a {(CO)4Cr} fragment.
Eu2Pt7AlP~3 und isotype Verbindungen: Eine neue Struktur aus CaBe2Ge2⁻ und Cu3Au-Einheiten / Eu2Pt7AlP~3 and Isotypic Compounds: A New Structure Containing CaBe2Ge2⁻ and Cu3Au-Type Units
Authors: Lux Christine , Wenski Guido , Mewis Albrecht
Published: March 2015

Eu2Pt7AlP~3 (a = 4.046(1) Å, c = 26.850(2) Å, Z = 2) and some isotypic compounds were prepared by heating the elements. They crystallize tetragonally (I 4/m m m) in a new intergrowth structure where segments occur with atom arrangements as in the CaBe2Ge2⁻ and Cu3Au-type.
Zur Kenntnis quaternärer Telluride Cu2MM′Te4 mit Tetraederstrukturen / Quaternary Tellurides Cu2MM′Te4 with Tetrahedral Structures
Authors: Haeuseler H. , Ohrendorf F. W. , Himmrich M.
Published: March 2015

Quaternary tellurides Cu2MM′Te4 (M = Zn, Cd, Hg and M′ = Si, Ge, Sn) have been prepared by solid state reactions and characterized by X-ray powder methods. All 9 compounds crystallize in a stannite type structure.
Monomere Komplexe des Vanadium(III) und -(IV) mit den Liganden 1,4,7-Triazacyclononan (L) und 1,4,7-Trimethyl-1,4,7-triazacyclononan (L′). Die Kristallstrukturen von [L′VF3] ·4 H2O und [L′V(acac)O](ClO4) / Monomeric Complexes of Vanadium(III) and -(IV) with the Ligands 1,4,7-Triazacyclononane (L) and 1,4,7-Trimethyl-1,4,7-triazacyclononane (L′). The Crystal Structures of [L′VF3] ·4Η2Ο and [L′V(acac)O](ClO4)
Authors: Knopp Petra , Wieghardt Karl , Nuber Bernhard , Weiss Johannes
Published: March 2015

The syntheses of monomeric complexes of V(III) and V(IV) containing the ligands 1,4,7-triazacyclononane (L) and its N-methylated derivative L′ are reported: [LVF3] · 0,5 H2O; [L′VF3]·4H2O; [L′V(acac)Cl]PF6; [LVOF2] · 2 H2O; [L′VO(acac)](ClO4). The crystal structures of [L′VF3]·4H2O and of [L′VO(acac)](ClO4) have been determined by X-ray crystallography. Electronic spectra, magnetic properties and the electrochemistry of these complexes are reported.
[Ph–C(NSiMe3)2]2FeCl; ein Amidinatokomplex von Eisen(III) mit verzerrt trigonal-bipyramidaler Struktur / [Ph–C(NSiMe3)2]2FeCl; an Amidinato Complex of Iron(III) with a Distorted Trigonal-Bipyramidal Structure
Authors: Zinn Alfred , Arnim Henning von , Massa Werner , Schäfer Michael , Pebler Jürgen , Dehnicke Kurt
Published: March 2015

The amidinato complex [Ph—C(NSiMe3)2]2FeCl has been prepared by the reaction of FeOCl with the amidine Ph—C(NSiMe3)[N(SiMe3)2] in acetonitrile/THF in the form of dark red moisture sensitive single crystals. The complex was characterized by IR spectroscopy, by its 57Fe-Mössbauer spectra, as well as by an X-ray structure determination. Space group PI, Z = 2, 3180 observed unique reflections, R = 0.068. Lattice dimensions at —80°C: a = 1210.4(2), b = 1272.7(3), c = 1316.0(3) pm; α = 67.81(3)°, β = 76.14(3)°, γ = 67.19(3)°. The complex has a molecular structure in which the iron atom is surrounded in a distorted trigonal-bipyramidal fashion with the chlorine ligand and two nitrogen atoms of different amidinato chelates in equatorial positions. The remaining nitrogen atoms occupy the apical positions.
Darstellung, Schwingungsspektren und Normalkoordinatenanalyse der Acetatochloroditechnetate(III), cis-Tc2(O2CCH3)2Cl4L2 (L = axiale Donorbase) sowie Kristallstruktur von cis-Tc2(O2CCH3)2Cl4((CH3)2NCOCH3)2 / Preparation, Vibrational Spectra and Normal Coordinate Analysis of Acetatochloroditechnetates(III), cis-Tc2(O2CCH3)2Cl4L2 (L = Axial Donorbase) and the Crystal Structure of cis-Tc2(O2CCH3)2Cl4((CH3)2NCOCH3)2
Authors: Skowronek J. , Preetz W. , Jessen S. M.
Published: March 2015

Tc2(O2CCH3)2Cl4(H2O)2 has been prepared by reaction of [Tc2Cl8]2- with acetic anhydride and fluoroboric acid. By treatment with the donor bases L = N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAA), dimethylsulfoxide (DMSO), triphenylphosphinoxide (TPO) and pyridine (Py), the green adducts Tc2(O2CCH3)2Cl4L2 are formed. The structure of Tc2(O2CCH3)2Cl4(DMAA)2 was determined by X-ray diffraction; space group C2/c with a = 29.604(4), b = 10.895(2), c = 14.404(2) Å, β = 97.87(2)°, Ζ = 8, Rw = 2.7%. The Tc-Tc distance is 2.1835(7) Å, the bridging acetate groups are in cis-positions. The IR and Raman spectra have been recorded at 80 K and assigned according to point group C2v, supported by a normal coordinate analysis of Tc2(O2CCH3)2Cl4(DMAA)2 based on a general valence force field. The stretching interaction constant fd(TcTc) is determined to 3.38 mdyn/Å. With increasing donor strength of the axial ligands, the intense Raman vibration v(TcTc), showing up to three overtones, is lowered from 311 to 282 cm-1. The δ-δ* transitions of all adducts are observed at 648-652 nm.
Synthese und Strukturen von Monoalkylamiden und -imiden des Titans / Synthesis and Structures of Monoalkylamides and -imides of Titanium
Authors: Bai Yüniu , Noltemeyer Mathias , Roesky Herbert W.
Published: March 2015

A new method for the preparation of monoalkylamides of composition Cp′TiCl2NHR is reported. Me3SnNHR (R = tBu 1a, CHiPr2 1b) reacts with Cp′TiCl3 with elimination of Me3SnCl to yield Cp′TiCl2NHR (2) (2a: Cp′ = C5H5, R = tBu, 2b: Cp′ = Me3SiC5H4, R = tBu, 2c: Cp′ = (Me3Si)2C5H3, R = tBu, 2d: Cp′ = Me4C5H, R = tBu, 2e: Cp′ = Me5C5, R = tBu, 2f: Cp′ = C5H5, R = CHiPr2, 2g: Cp′ = Me3SiC5H4, R = CHiPr2, 2h: Cp′ = (Me3Si)2C5H3, R = CHiPr2, 2i: Cp′ = Me4C5H, R = CHiPr2, 2j: Cp′ = Me5C5, R = CHiPr2). Compounds 2a-2j are stable and eliminate HCl only in the presence of a strong base to form (C5H5TiClNtBu)2 (3a) or (Me3SiC5H4TiClNtBu)2 (3b) from 2a and 2b, respectively. In 3a the chlorine atoms are substituted by NHtBu groups in boiling THF by means of LiNHtBu to give (C5H5TiNHtBuNtBu)2 (4). The reactions of 2e and 2b with LiN(SiMe3)2·Et2O in the presence of pyridine yield Me5C5TiClNtBu · Py (5a) (Py = pyridine) and Me3SiC5H4TiClNtBu·Py (5b), respectively. Compounds 2e and 5a have been characterized by X-ray crystal structural analysis.
Chiral Intermediates and the Oscillatory Effect of Circular Dichroism in the Belousov – Zhabotinskii Type Reaction of L-Ascorbic Acid
Authors: Buhse Thomas , Thiemann Wolfram
Published: March 2015

Investigating the Belousov—Zhabotinskii (BZ) type reaction of an acidic L-ascorbic acid (AA) / potassium bromate / cerous sulfate system, an oscillatory effect of circular dichroism is detectable at λ = 300 nm. HPLC analysis of the oscillatory mixture and spectroscopic experiments indicate that this effect is caused by 3,4,5-trihydroxy-2-oxo-L-valeraldehyde (TVA) — a C 5 oxidation fragment of AA. Because of the bromide ion production occurring before the metal catalyst addition the AA system shows no preoscillatory phase and a rather short entire length of oscillation up to a maximum of 20 min. Since AA is not brominated but oxidized by bromine which is formed by the Landolt typ “clock reaction” of AA with acidic bromate, partially bromine-hydrolysis-controlled (BHC) oscillations are discussed for the overall mechanism of this BZ system.
Durch Säuren katalysierte Öffnung eines Epoxids und Reaktionen der Produkte an Kieselgel / Acid Catalyzed Alcoholysis of an Epoxide and Reactions of Products on Contact with Silica Gel
Authors: Habermehl Gerhard G. , Wippermann Irene
Published: March 2015

The alcoholysis of epoxide 1 in acidic methanol leads to various products; one of these — hydroxymethoxyketone 7 — rearranges to the isomeric ketone 14 on contact with silica gel.
Übergangsmetallkomplexe mit Schwefelliganden, LXI / Transition Metal Complexes with Sulfur Ligands, LXI
Authors: Sellmann Dieter , Seubert Bernd , Kern Wolfgang , Knoch Falk , Moll Matthias
Published: March 2015

In order to study the properties of sulfur coordinated metal centres, the chromium and tungsten complexes [Cr(NO)(µ-′S4′)]2 (4), (NR4)2[W(NO)2(′S2′)2] (1) (R = Me (la), n-Bu (lb)), [W(NO)2(′S4′)] (2), [µ-O{W(NO)(′S4′)}2] (3) and [W(NPR3)(NO)(′S4′)] (5) (R = Me (5a), Et (5 b)) were synthesized (′S2
′2- = 1.2-benzenedithiolate(2-); ′S4
′2- = 1.2-bis(2-mercaptophenylthio)ethane(2-)). la and lb result from the reductive nitrosylation of Li2[W(′S2′)3] which was prepared by reduction of [W(′S2′)3] with n-BuLi. la was also obtained from [W(NO)2(Cl)2]n, ′S2
′2- and NMe4
+. Alkylation of la or lb by 1.2-dibromoethane yields 2, whose X-ray structure analysis shows that W is pseudooctahedrally coordinated by two trans thiolato S, two cis thioether S and two cis N atoms of linear W-NO groups. 2 was also obtained from [W(NO)2(CH3CN)4](BF4)2 or [W(NO)2(Cl)2]n and ′S4
′2--. The reaction of [W(NO)2(Cl)2]n yielded the dinuclear oxo-bridged complex 3 as a by-product in small amounts. In preparative amounts, 3 was synthesized by hydrolysis of [W(Cl)(NO)(′S4′)]. In contrast to the analogous Mo complex, 2 does not react with N2H4; with the ligands PMe3 and PEt3, it gives the corresponding phosphiniminato complexes 5 and free phosphineoxides OPR3. In order to compare the [M(NO)2(′S4′)] complexes (M = Cr, Mo, W), the structure of [Cr(NO)2(′S4′)] was determined by X-ray structure analysis. The Cr complex exhibits the same molecular coordination geometry as 2. While growing crystals of [Cr(NO)2(′S4′)], the dinuclear Cr complex 4 was also formed. Its X-ray structure analysis shows each of the Cr centres to be coordinated pseudooctahedrally by five sulfur donors and one nitrosyl N donor. 4 was also obtained by the reaction of [Cr(CO)4(nor)] with ′S4
′2- and NOBF4.
Synthese, Magnetismus und Kristallstruktur des trinuklearen Cu(II)-Komplexes [(LCu)2Cu(H2O)](ClO4)2 · 2 H2O (L = 4,7-Bis(2-hydroxybenzyl)-1-oxa-4,7-diazacyclononan) / Synthesis, Magnetism and Crystal Structure of the Trinuclear Cu(II)-Complex [(LCu)2Cu(H2O)](ClO4)2 · 2H2O (L = 4,7-Bis(2-hydroxybenzyl)-1-oxa-4,7-diazacyclononane)
Authors: Flaßbeck Claus , Wieghardt Karl , Nuber Bernhard , Weiss Johannes
Published: March 2015

The trinuclear copper(II) complex [(LCu)2Cu(H2O)](ClO4)2·2H2O (L = 4,7-bis(2-hydroxybenzyl)-1-oxa-4,7-diazacyclononane) has been synthesized and its crystal structure has been determined. From temperature dependent magnetic susceptibility measurements strong intramolecular antiferromagnetic coupling of the spins has been detected yielding an S = 1/2 ground state. The trinuclear species dimerizes in acetone solution to yield {[(CuL)2Cu]2}(ClO4)4 which has an S = O ground state.
Synthese und Struktur von 1,3,6,8-Tetra-tert-butylcarbazol / Synthesis and Structure of 1,3,6,8-Tetra-tert-butylcarbazole
Authors: Kuhn Norbert , Schulten Michael , Boese Roland , Bläser Dieter
Published: March 2015

The synthesis of 1,3,6,8-tetra-tert-butylcarbazole (2) by the reaction of carbazole with tertbutyl chloride in the presence of aluminium chloride is reported. The X-ray structures of 2 and its diethyl ether adduct are compared. The gap formed by the tert-butyl groups in 1,8-position has been calculated and compared with that of the supermesithyl substituent.
Preparative and Vibrational Spectroscopic Studies of Anilinium Salts Containing the [Hg2Cl6]2-, [Hg2Cl4X2]2-, [CdHgI6]2-, [CdHgI4Br2]2- and [CdHgBr4I2]2- Ions (X = Br, I)
Authors: Zafiropoulos Theodoros F. , Plakatouras John C. , Perlepes S. P.
Published: March 2015

Synthetic procedures are described that allow access to anilinium salts containing the complex anions [Hg2Cl6
2-, [Hg2Cl4X2]2- (X = Br, I), [CdHgI6]2-, [CdHgI4Br2]2- and [CdHgBr4I2]2--. Isolated dimeric structures are proposed for the new complexes in the solid state, using X-ray powder patterns, Far-IR and Raman spectra. The spectral detail is greatly enhanced in measurements at low temperature (∼100 K).
Sterische Effekte auf die Hydrierstabilität von 1, 1′-Dialkyl-4,4′-bipyridiniumsalzen (Viologenen) in wasserphotolytischen Systemen / Steric Effects on the Hydrogen Stability of 1,1′-Dialkyl-4,4′-bipyridinium Salts (Viologens) in Water Photolytic Systems
Authors: Bauer Rupert , Königstein Christian
Published: March 2015

The chemical stability of 1,1′-dialkyl-4,4′-bipyridinium compounds (viologens) as electron relay agents in hydrogen producing water photolytic systems is of great importance for practical applications. Three new 1,1′-dialkyl-4,4′-bipyridinium compounds (1 = 1,1′-dimethyl-2-phenyl-6-(p-tolyl)-4,4′-bipyridiniumdiperchlorate, 2 = 1,1′-dimethyl-2-phenyl-4,4′-bipyridiniumdiperchlorate, 3 = 6-phenyl-1,1′,2-trimethyl-4,4′-bipyridiniumdiperchlorate) have been investigated with respect to their stability and turnover numbers in a classical water photolytic system. H2 was detected during irradiation of solutions using Ru(bipy)3Cl2 as sensitizer, 1-3 as electron relay, EDTA as sacrificial electron donor, and a colloidal catalyst (platinum or palladium) with light λ > 400 nm. Quantum yields (platinum catalyst, light: 400-500 nm) were 18% 1 and 3, 16% 2, compared with methylviologen: 16%. The loss of 1,1′-dialkyl-4,4′-bipyridinium compounds due to hydrogenation was monitored by HPLC. Turnover Numbers (only hydrogen in gas phase was taken into account) were found to be 82 1, 64 2, 57 3 as compared with 39 for methylviologen. Using palladium or palladium supported on BaSO4 instead of platinum as catalysts did not increase the turnover numbers.
Bicyclo[2.2.2]octane-2-spirocyclohexanes, Part 2[1]. Reduction Products of Spirodiisophora-3′,6-dione
Authors: Kurzer Frederick , Kapadia Zakir
Published: March 2015

The reduction of spirodiisophora-3′,6-dione under various conditions occurs exclusively at its 3′-keto-function in the cyclohexane ring. The action of lithium aluminium hydride yields the 3′-eq-hydroxyketone, while catalytic hydrogenation, hydroboration and the action of metal borohydride produces the 3′-ax-epimer. The conformers give rise to pairs of distinct epimeric functional derivatives. Anhydrous hydrazine removes the 3′-oxygen function of the 3′,6-dione entirely, with formation of spirodiisophor-6-one. Catalytic hydrogenation of the 3′-oximino-6-ketone yields the corresponding 3′-amine. The 13C NMR spectra of the individual products are assigned and correlated with their structures.
Notizen: Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXXII. / Novel Basic Ligands for the Homogeneous Catalytic Carbonylation of Methanol, XXXII.
Authors: Lindner Ekkehard , Reber Jens-Peter
Published: March 2015

The (ether-phosphine)cobalt(II) complexes I2Co[D~P(Ph)CH2CH2P(Ph)~D] (3a) [D = CH2C4H7O2 (a)] and I2Co(Ph2P~D)2 (6b,c) [D = CH2C5H9O (b), CH2C3H5O2 (c)] are obtained by reaction of CoI2 with the ligands D~P(Ph)CH2CH2P(Ph)~D (1a) and Ph2P~D (2b,c). Reduction of 3a and 6b, c with K[HB(sec-C4H9)3] results in the formation of the cobalt(I) complexes ICo[D⁀P(Ph)CH2CH2P(Ph)~D] (4a) and ICo(D⁀PPh2)(D~PPh2) (7b,c) (D~P: η1-P coordinated; D⁀P: η2-O,P coordinated). 4a and 7b, c are precatalysts in the carbonylation and hydrocarbonylation of methanol to methyl acetate and acetaldehyde, respectively. The weak Co-O bond is cleaved by reaction of 4a and 7b, c with CO to give the dicarbonyl cobalt complexes 5a and 8b,c.
Übergangsmetallkomplexe mit Schwefelliganden, LXXVI Redox- und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (NMe4)2[Ni(′S2′)2] und [Ni(′S4 – C3′)(PMe3)] / Transition Metal Complexes with Sulfur Ligands, LXXVI Redox and Addition Reactions of Nickel Complexes with Multidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (NMe4)2[Ni(′S2′)2] and [Ni(′S4–C3′)(PMe3)]
Authors: Sellmann Dieter , Fünfgelder Stefan , Knoch Falk , Moll Matthias
Published: March 2015

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).

Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.

The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.
Neutrale und kationische Eisen-Schwefel-Komplexe und -Cluster Synthese und Kristallstrukturen von [Fe(SR)2L2] · PhMe und [Fe4S4(SR)2L2] sowie zur Bildung von [Fe(SR)L3]+, [FeL4]2+, [Fe4S4(SR)L3]+ und [Fe4S4L4]2+ (R = 2,4,6-i-Pr3C6H2; L = SC(NMe2)2) / Neutral and Cationic Iron-Sulfur Complexes and Clusters Syntheses and Crystal Structures of [Fe(SR),L2] · PhMe and [Fe4S4(SR)2L2], and on the Formation of [Fe(SR)L3]+, [FeL4]2+, [Fe4S4(SR)L3]+ and [Fe4S4L4]2+ (R = 2,4,6-i-Pr3C6H2; L = SC(NMe2)2)
Authors: Bierbach Ulrich , Saak Wolfgang , Haase Detlev , Pohl Siegfried
Published: March 2015

The reaction of [FeI2L2] (1; L = SC(NMe2)2) with KSR (R = 2,4,6-i-Pr3C6H,) yields [Fe(SR)2L2] · PhMe (2).

Oxidation of the thiolate ligands of 2 with ((Me2N)2CSSC(NMe2)2)2+ affords the cationic complexes [Fe(SR)L3]+ and [FeL4]2+, which were isolated as tetraphenylborate salts.

A mixed ligand neutral iron sulfur cluster [Fe4S4(SR)2L2] (3) has been synthesized by the reaction of 2 with elemental sulfur. 3 is a precursor for cationic clusters which are obtained via the above-mentioned oxidation. The structures of 2 and 3 were determined from single crystal X-ray diffraction data.

2 crystallizes in the monoclinic space group C2/c with a = 1807.8(1), b = 1000.6(1), c = 2946.0(2) pm, β = 101.16(1), V = 5227.6 × 106 pm3, Ζ = 4, R = 0.067. The complex exhibits C2-symmetry and a distorted tetrahedral coordination of Fe(II) (S–Fe–S angles between 101.7 and 125.7). The Fe–Sthiourea and Fe–Sthiolate bond lengths were found to be 240.3(2) and 231.5(1) pm, respectively.

3: triclinic, P1, a= 1020.2(2), b = 1035.3(2), c = 1402.1(2) pm, α = 73.50(1), β = 70.47(1), γ=84.38(1),V= 1338.2 × 106pm3,Z= 1, R = 0.039.

3 shows a slightly compressed Fe4S4 core structure. The Fe– Fe distances range from 269.1 to 278.1 pm. The shortest and longest distances are observed between those Fe atoms which have two thiourea and two thiolate ligands, respectively.
Darstellung und Eigenschaften von Bis(phthalocyaninato)lanthanaten und -ceraten / Preparation and Properties of Bis(phthalocyaninato)lanthanates and -cerates
Authors: Haghighi Mohsen Safarpour , Homborg Heiner
Published: March 2015

High yields of bisphthalocyaninates of lanthanum and cerium have been obtained in the strongly exothermic reaction of the dehydrated lanthanoid acetates with molten 1,2-dicyanobenzene in the presence of potassium hydroxide or methylate. Salts of the type (cat)[M(Pc(2—)),] (M = La, Ce) with different cations (cat+ = K, Bu4N, PNP, TDOA) have been isolated. The corresponding “Hydrogen salts” are obtained by thermal decomposition of (Bu4N)[M(Pc(2—))2] at T > 350 C. The dimeric structure is confirmed by negative fast atom bombardement mass spectra. The redox properties have been investigated by cyclovoltammetry and UV, VIS, MIR, FIR and resonance Raman (RR) spectra are reported. Electronic transitions between 2000 and 3000 cm-1 are observed in the low temperature RR spectra of (Bu4N)[Ce(Pc(2—))2] being RR enhanced at 470 nm. From the assignment to the higher transitions within the symmetry split 5F5,2,,2F72 manifolds of the f1 ground state of Ce3+ the crystal field parameters ζ4f = 610.5, B40 = 242.2 and B60 = 4.1 cm-1 have been determined.
Crystal and Magnetic Structures of NaMnF4
Authors: Molinier Michel , Massa Werner , Khairoun S. , Tressaud A. , Soubeyroux J. L.
Published: March 2015

An X-ray single crystal structure determination (monoclinic, space group P21/c, a = 573.6(2), b = 489.2(1), c = 574.8(2) pm, β = 108.07(2), Z = 2; wR = 0.038 for 380 reflections) shows that NaMnF4 crystallizes in the same layered structure type as LiMnF4. In the quadratic layers the Mn-F-Mn bridges are strongly asymmetric, due to the Jahn-Teller effect, leading to an antiferrodistortive order of elongated octahedra. The bridging angle is 138.4°. The Na+ ions are 6-coordinated as well. The common structural arrangement of both [MnF6] and [NaF6] octahedra shows topological relation to the rutile structure. In the magnetic measurements performed on powder samples NaMnF4 behaves as an antiferromagnet with a weak ferromagnetic component below 13 K. By neutron diffraction on powder (4-70 K) a magnetic cell doubled along the α-axis is found and below a Neel temperature of TN = 13 K the magnetic structure shows colinear antiferromagnetic arrangement of the spins pointing slightly (16) out of the layer plane. The resulting magnetic moment is 3.52 μΒ.
Synthese und Kristallstruktur von Bis(o-aminobenzonitril)-diquecksilber(I)-dinitrat / Synthesis and Crystal Structure of Bis(o-aminobenzonitrile)dimercury(I)-dinitrate
Authors: Brodersen Klaus , Hofmann Jürgen
Published: March 2015

[Hg2(o-NH2C6H4CN)2](NO3)2 is formed by the reaction of o-aminobenzonitrile with dimercury(I)-dinitrate in methanol. It crystallizes in the monoclinic space group P 2/c with a = 8.6819(5)Å, b = 5.3696(6)Å, c = 19.7645(8)Å, β = 95.138(12)° and Ζ = 2. The crystal structure has been determined by single crystal X-ray diffraction with applied gaussian absorption correction and refined to an Rw-value of 0.027.

The Hg2
2+-ion is coordinated to both amino nitrogen atoms. Strong hydrogen bonds and bridging nitrate ions lead to chain structure.
Chemie polyfunktioneller Moleküle, 108 Tetraedrische Kupfer(I)-Chelatkomplexe der Liganden Bis(diphenylphosphino)amin und Bis(diphenylphosphino)methan / Chemistry of Polyfunctional Molecules, 108 [1] Tetrahedral Copper(I) Chelate Complexes with the Ligands Bis(diphenylphosphino)amine and Bis(diphenylphosphino)methane
Authors: Ellermann Jochen , Knoch Falk A. , Meier Klaus J.
Published: March 2015

Reaction of [Cu(PPh3)2(NO3)] (1) in acetone with bis(diphenylphosphino)amine (dppa, 2) yields [Cu(dppa)(PPh3)2]+NO3
- (3a). [Cu(dppa)(PPh3)2]+PF6
- (3b) has been synthesized by metatheses of 3a with NH4PF6. The salt [Cu(dppm)(PPh3)2]+PF6
- (5b) has been prepared by an one batch reaction of [Cu(PPh3)2(NO3)] (1), bis(diphenylphosphino)methane (dppm, 4) and NH4PF6 in methanol, because [Cu(dppm)(PPh3)2]+NO3
- (5a) could not be isolated by the direct reaction of 1 with 4. The IR, Raman, 31P{1H} NMR, 1H{31Ρ} NMR as well as the conductivity data are reported and discussed together with the X-ray crystal structure of 3a · 1.8 (CH3)2CO. The structure consists of copper atoms coordinated tetrahedrally by two PPh3 ligands and the chelating dppa ligand and features a highly strained four-membered ring. The distorted tetrahedral cations are hydrogen bridged to the nitrate anions. The colourless needles of 3a· 1.8 (CH3)2CO crystallize in the monoclinic space group C 2/c, with the lattice constants a = 4189.2(27); b = 1223.7(8); c = 2717.8(15) pm;β = 113.16(4)°.
Notizen: Darstellung und Charakterisierung von K3O(CN) / Preparation and Characterization of K3O(CN)
Authors: Hardt Christian , Vogt Petra , Sabrowsky Horst
Published: March 2015

The colourless compound K3O(CN) has been prepared. The characterization by X-ray powder methods leads to a cubic primitive lattice (Pm 3m) with a = 520(2) pm (Z = 1). The structure is related to the anti-perovskite type.
Asymmetrische Katalysen, 76. Rh-katalysierte enantioselektive Hydrosilylierung von Acetophenon mit einem polymergebundenen Pyridinoxazolin / Asymmetric Catalysis, 76. Rh-Catalyzed Enantioselective Hydrosilylation of Acetophenone by a Polymer-Bound Pyridineoxazoline
Authors: Brunner Henri , Brandl Paul
Published: March 2015

In the enantioselective hydrosilylation of acetophenone with diphenylsilane, a polystyrenebound heterogeneous Rh/pyridineoxazoline catalyst achieved higher optical inductions than a comparable homogeneous catalyst. After using the polymeric catalyst 8—10 times, the catalytic activity decreased markedly and an inversion of the product configuration was observed, the enantiomeric excess rising to 92% ee. These results indicate that the polymeric catalyst contains several catalytically active species with different enantioselectivity and stability.
15N Nucelar Magnetic Resonance Study of Two-Coordinate Phosphorus Cations - Sign-Determination of Coupling Constants – Application of Two-Dimensional (2D) Heteronuclear Shift Correlations
Authors: Wrackmeyer Bernd , Schiller Jürgen
Published: March 2015

Cyclic and non-cyclic bis(amino)phosphenium cations (1 to 4) together with their precursors (bis(amino)phosphorus chlorides 5 to 8) and some other bis(amino)phosphorus compounds (9 to 14) have been studied by 13C, 15N (natural abundance), 29Si and 31P NMR spectroscopy. 15N chemical shifts and coupling constants 1J(31P15N) of phosphenium cations have been determined for the first time. NMR data of 1 to 4 are compared with those of a bis(amino)carbene and various bis(amino)stannylenes. In the phosphenium cations 1 to 4 the 15N nuclear shielding is considerably reduced (ca. 70 to 100 ppm as compared with 5 to 14) and there is a crude linear relationship between δ15N and δ31P values. Changes in the δ15N values of 1 to 4 do not reflect P-N (pp)π interactions. A positive sign has been determined for the coupling constants 1J(31Ρ15Ν) [reduced coupling constants 1K(31P15N) < O] for the phosphenium cations and for all other P(III)-N compounds studied. This was achieved by applying various one- and twodimensional heteronuclear double resonance techniques. The experiments also gave signs of the coupling constants 2J(31PN13C), 2J(31PN29Si), 3J(31PNC13C), 3J(31PNSi13C), 4J(31PNCC1H) and 4J(31PNSiC1H). Negative contributions to 1K(31P15N), arising from the lone pair of electrons at phosphorus, are more noticeable in the case of the phosphenium cations.
Darstellung, Reaktivität und Kristallstruktur von [(CO)3Mn(dppm)2(μ-S)Rh(CO)] / Synthesis, Reactivity and Crystal Structure of [(CO)3Mn(dppm)2(μ-S)Rh(CO)]
Authors: Heyke O. , Beuter G. , Lorenz I.-P.
Published: March 2015

The reaction of [(CO)3Mn(dppm)2Rh(CO)] (1) with H2S in dichloromethane yields [(CO)3Mn(dppm)2(μ-S)Rh(CO)] (2), which is characterized by IR, 31P{1H}, 1H, 13C{1H} nmr and mass spectra. The crystal structure of 2 was determined by X-ray diffraction: space group P21/n, Z = 4, a = 1232.6(3), b = 2558.8(4), c = 1640.8(2) pm, β = 97.74(2)°, R/Rw = 0.048/0.057. The dimeric complex shows A-frame structure possessing a bridging sulfur and a semibridging CO group. 2 cannot be oxidized to the corresponding SO2 bridged complex [(CO)3Mn(dppm)2(μ-SO2)Rh(CO)] (3). The reaction of 2 with SO2, however, yields the SO2 bridged complex [(CO)2Mn(dppm)2(μ-S)(μ-SO2)Rh(CO)] (5); in dichloromethane 2 is readily chlorinated to afford the salt [(CO)3Mn(dppm),(μ-S)RhCl]Cl (4).
Benzo-1,3,2-diselenazol-2-ylium-Salze – Synthese und Reaktivität / Benzo-1,3,2-diselenazolylium Salts – Synthesis and Reactivity
Authors: Wolmershäuser Gotthelf , Kaim Wolfgang , Heckmann Gert , Lichtblau Alexander
Published: March 2015

Benzo-1,3,2-diselenazolylium chloride can be prepared analogously to the corresponding sulfur compound. The cation has been characterized as its perchlorate by X-ray structure analysis. Reduction via the unstable neutral radical state finally affords the nitrogen-free ‘dibenzotetraselenocine’.
Die Kristallstrukturen von PPh4[AsCl4(THF)2] und PPh4[AsBr4(THF)2] / The Crystal Structures of PPh4[AsCl4(THF)2] and PPh4[AsBr4(THF)2]
Authors: Siewert Birgit , Müller Ulrich
Published: March 2015

In the effort to react W(CO)6 with (PPh4)2[As2Cl8] and Cr(CO)6 with PPh4[As2SBr5] in tetrahydrofurane under UV irradiation the title compounds were obtained as main products. Their crystal structures were determined by X-ray diffraction. PPh4[AsCl4(THF)2], monoclinic, P2/c, Z = 2, a = 881.6(3), b = 809.0(6), c = 2418.6(9) pm, β = 99.44(4)°, R = 0.086 for 1619 observed unique reflexions. PPh4[AsBr4(THF)2], monoclinic, C 2/c, Z = 4, a = 2459.2(5), b = 748.2(3), c = 1784.3(4) pm, β = 94.02(2)°, R = 0.080 for 1513 reflexions. In both compounds ions [AsX4(THF)2]- are located on inversion centers; they have octahedral coordination with trans configuration; the stereochemical activity of the lone electron pairs does not show up in deviations of the bond angles, but in increased bond lengths. The PPh4
+ ions are stacked to columns in the b direction.
Synthese und Kristallstrukturen von Tris(glykolato)molybdän(VI) und Tris(pinakolato)molybdän(VI) / Syntheses and Crystal Structures of Tris(glycolato)molybdenum(VI) and Tris(pinacolato)molybdenum(VI)
Authors: Buth Silke , Wocadlo Sigrid , Neumüller Bernhard , Weller Frank , Dehnicke Kurt
Published: March 2015

PPh4[MoN(OPh)4] has been prepared by reaction of PPh4[MoNCl4] with sodium phenolate, as an orange-red crystal powder. The reactions of glycole and pinacole, respectively, with MoN(O-t-Bu)3 and MoNCl3, the latter in the presence of a base, lead to the tris-chelate complexes Mo(OC2H4O)3 and Mo(OC2Me4O)3, respectively. The complexes were characterized by 1H and 13C NMR spectroscopy, the chelate complexes in addition by X-ray structure analysis.

[Mo(OC2H4O)3]: Space group P21/c, Z = 4, 2177 observed unique reflections, R = 0.047. Lattice dimensions at –40 °C: a = 1168.3(2), b = 716.0(1), c = 1206.1(2) pm, β = 92.84(1)°. [Mo(OC,Me4O)3] • 2CH2Cl2: Space group P bcn, Z = 4, 1860 observed unique reflections, R = 0.049. Lattice dimensions at –80°C: a = 1772.3(1), b = 1023.8(1), c = 1600.0(2) pm.

Both complexes form monomeric molecules, in which the molybdenum atoms are surrounded in a distorted octahedral fashion by the six oxygen atoms of the chelates.
Kristallstruktur und molekulare Dynamik eines Stereoisomeren von (P,P′,P″,P‴-Tetraphenyl)-1,1,2,2-ethantetrakisphosphinsäuretetraisopropylester / Crystal Structure and Molecular Dynamics of a Stereoisomer of (P,P′,P″,P‴-Tetraphenyl)-1,1,2,2-ethane-tetraphosphinic Acid Tetraisopropylester
Authors: Hägele Gerhard , Reinemer Peter , Batz Michael , Mootz Dietrich
Published: March 2015

The crystal and molecular structure of (P,P′,P″,P‴-tetraphenyl)-1,1,2,2-ethane-tetraphosphinic acid tetraisopropylester has been determined from single-crystal MoKa diffractometer data. The crystals are monoclinic with space group C 2/c, Ζ = 4, a = 2054.5(9), b = 1189.8(5), c = 1800.8(8) pm, β = 110.07(3)°. The structure was solved by direct methods and refined to R = 0.046. A 250 ps-vacuo-trajectory was calculated using the Molecular Dynamics program GROMOS. Structural data and MD results are compared to NMR spectroscopic data. A Karplus-type relation was confirmed for coupling constants 3JPP.
Das 7,8-Benzo-5-chloro-1,4,4-trimethyl-1-aza-4-azonia-6,9-dioxa-5 λ5-phosphaspiro[4.4]nonanyl-Kation: Röntgenstrukturanalyse und temperaturabhängige 1H-NMR-Spektren: The 7, 8-Benzo-5-chloro-1,4,4-trimethyl-1-aza-4-azonia-6,9-dioxa-5 λ).5-phosphaspiro[4.4]nonanyl Cation: X-Ray Crystal Structure Determination and Variable 1H NMR Spectra
Authors: Kaukorat Thomas , Jones Peter G. , Schmutzler Reinhard
Published: March 2015

The 1H NMR spectrum of the spirophosphorane 3 at room temperature indicates dynamic behaviour of the cation. The low-temperature 1H NMR spectra of 3 exhibit two sets of doublets for the protons of the diastereotopic N(CH3)2 groups. The free enthalpy of activation for the dynamic process was determined (58.6 KJ/mole). In the reaction of 3 with sodium tetraphenylborate the crystalline compound, 4, involving the non-coordinating anion, [B(C6H5)4]-, was obtained. The X-ray crystal structure analysis of 4 reveals the presence of a five-membered ring, formally as a result of intramolecular donor-acceptor interaction between the nitrogen atom of the N(CH3)2 group and phosphorus. The geometry at phosphorus deviates somewhat from ideal trigonal bipyramidal.
Complexes of (CF3)3B with Sterically Crowded Amines. Unexpected Side Products from the Trifluoromethylation of Cl2BN(t-Bu)(Bz). Crystal and Molecular Structures of (CF3)3BNH(CH2)6, HO(CF3)2BCH(Ph)NH(t-Bu)(Bz) and Ph(CF3)2BCHN(t-Bu)(Bz)
Authors: Ansorge Andreas , Brauer David J. , Bürger Hans , Dörrenbach Frank , Krumm Burkhard , Pawelke Gottfried
Published: March 2015

Trifluoromethylation of C12BN(CH2)6, Cl2B(tmp), tmp = 2,2,6,6-tetramethylpiperidino, and Cl2BN(t-Bu)(Bz) with three equivalents of CF3Br/P(NEt2)3 yields the amine complexes (CF3)3B · NH(CH2)6 (1), (CF3)3B ·NH2CMe2(CH2)2CHCMe2 (2) and (CF3)3B · NH2(Bz) (3). The preparation of 3 was accompanied by formation of three unexpected trifluoromethylboron derivatives X(CF3)2BCH(Ph)NH(t-Bu)(Bz) (D), X = Br (4), Cl (5), and (Ph)(CF3)2BCHN(t-Bu)(Bz) (6), the latter being formed from 4 by HBr elimination and rearrangement. Reaction of 4 with H2O, EtOH, HCONMe2 and Me3SnH yielded D, X = OH (7), EtO (8), HCOO (9), and (Ph)(CF3)2BCH2NH(t-Bu)(Bz) (10), respectively. The structures of 1, 6 and 7 have been determined by X-ray diffraction analysis.
Reaction between Superoxide Anion and Several Oxovanadium(IV) Compounds
Authors: Nishida Yuzo , Tokii Tadashi , Watanabe Izumi
Published: March 2015

We have observed that the superoxide anion reacts with VO(salen), but not with VO(saldpt), where H2(salen) and H2(saldpt) are Schiff base ligands derived from salicylaldehyde and ethylenediamine or dipropylenetriamine, respectively. Based on the electrochemical, ESR, and UV spectroscopic studies of the reaction mixture, it was concluded that the superoxide anion reacts with VO(salen) to oxidize V(IV) to V(V) through the formation of a vanadium(V)-peroxide adduct with side-on configuration. The SOD-like function of VO(salen) was elucidated in terms of the above assumption.
The Effect of Quinolyl Endgroups on Podand Fluctuations-1-DNMR and 2D-EXCSY-NMR of Co(II)-Complexes
Authors: Dickert Franz L. , Feigl Matthias , Gmeiner Wolfgang , Meißner Harald U.
Published: March 2015

Ligand fluctuations in complexes [Co(Kr5)]X2 (Kr 5 = 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane) with X = ClO4
-, CF3SO3
- can be detected by NMR spectroscopy above room temperature in inert solvents such as nitromethane. This unusually slow ligand movement is due to the strong coordination of the quinolyl end groups to the Co(II) ion as demonstrated through measurements with oligo-ethylene-glycols. In contrast to the 13C spectra, the 1H 2 D EXCSY NMR spectra reveal cross peaks which are due to a magnetisation exchange between the chemically non-equivalent protons in the -CH2- groups of the podand. This process is associated with a movement of the chain segments towards each other.
Darstellung und Kristallstruktur von [Co2(CO)6(μ-S2)]2+(AsF6
-)2 · 1/2 SO2
Preparation and Crystal Structure of [Co2(CO)6(μ-S2)]2+(AsF6
-)2 · 1/2SO2
Authors: Minkwitz Rolf , Borrmann Horst , Nowicki Joachim
Published: March 2015

[Co2(CO)6(μ-S2)]2+(AsF6-)2· 1/2SO2 is formed in the reaction of S8
2+(AsF6-)2 with Co2(CO)8 in SO2 at R.T.. The complex crystallizes in the orthorhombic space group Pbcn (No. 60) with a = 1508.0(9), b = 1642.7(8), c = 871.3(6) pm, V = 2158(2)•106 pm3, Z = 4. In the tetrahedral Co2S2 unit a short S–S distance (198 pm) is observed.
Reaktionen von Oxo-Rhenium- und Diazenido-Rhenium-Komplexen mit funktionalisierten Hydrazinen. Kristall- und Molekülstrukturen von [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · .OPPh3 · MeOH, ReO(HNNC(S)Ph)(HNNHC(S)Ph), ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(S)Ph) und ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(O)SMe) / Reactions of Oxo and Diazenido Complexes of Rhenium with Functionalized Hydrazines. Crystal and Molecular Structures of [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · .OPPh3 · MeOH, ReO(HNNC(S)Ph)(HNNHC(S)Ph),ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(S)Ph) and ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(O)SMe)
Authors: Möhlenkamp Alfons , Mattes Rainer
Published: March 2015

The reaction of thiobenzoylhydrazine with ReO2I(PPh3)2 and Re2O3(S2CNEt2)4 yields [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · OPPh3 · MeOH (1), ReO(HNNC(S)PhXHNNHC(S)Ph) (2) and Re(HNNC(S)Ph)2(S2CNEt2) (3). Re(NNC(S)OMe)(S2CNEt2)2 (4) is obtained from O-methylthiocarbazate and Re2O3(S2CNEt2)4· ReCl2(PPh3)2(NNC(O)Ph) reacts with functionalized hydrazines H2NNHR (R = C(S)Ph, C(S)OMe, C(O)SMe, C(S)SMe) to the diazenidohydrazino complexes ReCl2(PPh3)2(NNC(O)Ph)(H2NNHR) (5-8). The structures of 1, 2, 5 and 6 have been determined. 1: monoclinic, space group Cc, a = 1892.1(2), b = 1227.3(1), c = 1858.4(2) pm, β = 98.34(1)°, Ζ = 4, 4544 reflections, R = 0.034; 2: monoclinic, space group P21, a = 938.6(2), b = 637.0(1), c = 1356.0(3) pm, β = 98.96(3)°, Ζ = 2, 1905 reflections, R = 0.026; 5: triclinic, space group P1̄, a = 1236.4(2), b = 1414.8(2), c = 1780.8(3) pm, α = 111.02(2)°, β = 98.19(2)°, γ = 108.29(1)°, Ζ = 2, 4576 reflections, R = 0.067; 6: triclinic, space group P1̄̄, a = 1185.9(2), b = 1195.8(2), c = 1625.4(3) pm, a = 96.36(3)°, β = 99.54(3)°, γ = 103.93(3)°, Ζ = 2, 8006 reflections, R = 0.032. 1 and 2 contain N,S-chelating HNNR and HNNHR ligands. The ligand structures can be considered as intermediate between hydrazido(2—) or (1—) and diazene or protonated diazene type structures. In 5-8 the hydrazine derived ligands are monodentate N-coordinated.
Torsional Isomerism of Bent Metallocene Complexes The Molecular Structure of Bis(isopropylcyclopentadienyl)zirconiumdichloride in the Solid State
Authors: Krüger Carl , Nolte Matthias , Erker Gerhard , Thiele Sven
Published: March 2015

Bis(isopropylcyclopentadienyl)zirconiumdichloride (1) was synthesized by the reaction of isopropylcyclopentadienyl lithium with 1/2 molar equivalent of zirconiumtetrachloride and then crystallized from methylenechloride. Complex 1 crystallizes in space group C2/c with cell parameters a = 24.492(3)A, b = 13.525(1)Å, c = 22.894(3)Å, β = 117.90(1)°, Z = 16, R = 0.046, Rw = 0.057. There are three independent molecular entities of 1 in the asymmetric unit. These represent torsional isomers differing in the relative positions of the isopropyl substituents at the Cp-rings. The three torsional isomers may be described as anti-, syn-, and gauchelike metallocene rotamers.
Preparation and Structure of Ethyl 4-Bromo-2-(diphenylmethylene)-3-oxo-5,5-diphenyl-4-pentenoate
Authors: Strelow Thomas , Voss Jürgen , Adiwidjaja Gunadi
Published: March 2015

Ethyl 4-bromo-2-(diphenylmethylene)-3-oxo-5,5-diphenyl-4-pentenoate (2) is formed on reaction of 2,4-bis-(diphenylmethylene)-1,3-cyclobutane dione (1) with bromine in the presence of ethanol. 2, C32H25BrO3, was characterized by X-ray structure analysis. Space group (orthorhombic) PNa21, Z = 8, a = 3459.3(2), b = 989.9(1), c = 1541.0(1) pm, R = 0.084.
Notizen: [K(18-Krone-6)][WF5(NCl)]; Synthese und Kristallstruktur / [K(18-Crown-6)][WF5(NCl)]; Synthesis and Crystal Structure
Authors: Stenger Harald , Dehnicke Kurt , Hiller Wolfgang
Published: March 2015

[K(18-crown-6)][WF5(NCl)] has been prepared as yellow crystals by the reaction of KF with WCl4(NCl) in the presence of 18-crown-6 in acetonitrile solution. The compound was characterized by its IR spectrum and by an X-ray structure determination. Space group P21/n, Z = 4, 3697 observed unique reflections, R = 0.034. Lattice dimensions at –65 °C: a = 1313.8(3), b = 851.2(1), c = 1842.7(4) pm, β = 95.304(1)°. The compound forms ion pairs, in which the pottassium ion is coordinated by the six oxygen atoms of the crown ether molecule and by two fluorine ligands of the [WF5(NCl)]- unit with K–F distances of 272.4(5) and 288.6(5) pm. The W=N–Cl group of the anion is nearly linear (bond angle 170.7(5)°) with bond lengths of WN = 172.4(7) and NCI = 162.7(7) pm.
Pentamethylcyclopentadienyl Halfsandwich Complexes of Rhodium and Iridium Containing 1,1′-Ferrocene Dichalcogenido Ligands
Authors: Herberhold Max , Jin Guo-Xin , Rheingold Arnold L. , Sheats George F.
Published: March 2015

A series of 12 bimetallic complexes Cp M(L)[(EC5H4)2Fe] (M(L) = Rh(PMe3), Ir(PMe3), Ir(PPh3) and Ir(CNtBu); E = S, Se, Te) has been synthesized from the dichlorides Cp M(L)Cl2. The new compounds have been characterized by their 1H, 13C and 31P NMR spectra in solution. The mass spectra indicate that the two-electron ligand L is preferentially eliminated upon electron-impact. Oxidation by AgBF4 to give ferrocenium-type cations also occurs readily. An X-ray structure analysis of CpRh(PMe3)[(SC5H4)2Fe] (la) confirms the presence of a 1,1′-ferrocene dithiolate ligand with parallel and ecliptic cyclopentadienyl rings. The long Rh ... Fe (430.4(1) pm) distance rules out any direct interaction between the rhodium center and the iron in the cavity of the ferrocene sandwich.
Metallkomplexe mit funktionalisierten Schwefelliganden, IV / Metal Complexes of Functionalized Sulfur-Containing Ligands IV
Authors: Weigand Wolfgang , Bosl Gabriele
Published: March 2015

The platinum(O) compound (Ph3P)2Pt(η2H4) (1) reacts with N-(alkyl- and arylsulfinyl) phthalimides R—S(O)-Nphth [R = C3H7 (2a), C4H9 (2b), C12H25 (2c), CH2Ph (2d), Ph (2e) p-CH3C6H4 (2f)] to give the trans-configurated sulfenato complexes (Ph3P)2Pt[S(O)—R](Nphth) (3a—f). The compounds 3a—f have been characterized by IR, 1H, 13C and 31P NMR spectroscopy, 3d—f additionally by their FAB mass spectra. The oxidation of cis-(Ph3P)2Pt(SC4H9)(Nphth) (5) with m-chloroperbenzoic acid leads to a mixture of compounds containing cis-(Ph3P)2Pt[S(O)C4H9](Nphth) (6) as a main product.
Cyclic Oligophosphonic Anhydrides Stable in Aqueous Media
Authors: Alferiev Ivan S. , Bobkov Sergey Yu.
Published: March 2015

Depending on reaction conditions, the phosphonylation of N-alkylacetamides with H3PO3– PCl3 in B · HCl media (B = Py, Bu3N) gives either 1-alkylaminoethylidene-1,1-bisphosphonic acids (la–e) or previously unknown 1-alkylaminobutane-1,1,3,3-tetrayl-tetrakisphosphonic dianhydrides (2a–e). The latter convert into monocyclic forms (3a–e) under mild acidic hydrolysis. Acyclic forms (4a–e) cannot be isolated. In the presence of higher N,N-dialkylamides the phosphonylation of acetamides affords the higher dianhydrides (2f–h). Strong acidic hydrolysis of 2 or 3 yields 3,3-diphosphonocarboxylic acids (5a–c). Reacting with H3PO3–PHal3 in B · HHal (Hal = Cl, Br), the amides R1CONHR2 (R1 ≠ H, Me; R2 = Alk, H) give both N-alkyl- (or N-unsubstituted) 1-aminoalkylidene-1,1-bis-phosphonic acids (6a–j) and their cyclic dimeric anhydrides (7a–g, i, j).
Gold Chains and Gold Pairs in the Layer Structure of 1,1,1-Tris[chloro-gold(I)-dimethylphosphanylmethyl]ethane
Authors: Stützer Albert , Bissinger Peter , Schmidbaur Hubert
Published: March 2015

The title compound, 1,1,1-tris[chloro-gold(I)-dimethylphosphanylmethyl]ethane (1) has been prepared from the tripodal tertiary phosphine ligand and three equivalents of chloro(dimethylsulfide)gold(I) in good yield. The complex has been characterized by means of its 1H, 13C, and 31P NMR, and 197Au Mößbauer spectra, by elemental analysis, and by a single crystal X-ray structure analysis. The crystals have a layer structure. In each of the crystallographically equivalent individual molecules two of the gold(I) centers are associated via a short intramolecular Au · · · Au contact [3.077(2) Å]. These pairs of gold atoms are aligned in chains through intermolecular Au ··· Au contacts of similar distances [3.084(2) Å]. According to this structural principle, strings of complex molecules are formed. The third Au(I) center of each of these molecules is associated with a similar unit of a neighbouring chain through interstrand Au ··· Au contacts [3.179(3) Å], thus crosslinking the chains to give a layer structure. The Au · · · Au contacts are recognized to be the main structure-determining force for the conformation of the molecules and their packing in this solid phase.
[Fe4S4I2(C6H10(NHCSNHMe)2)]: ein neutraler Eisen-Schwefel-Cluster mit zweizähnigem Liganden / [Fe4S4I2(C6H10(NHCSNHMe)2)]: A Neutral Iron-Sulfur Cluster with a Bidentate Ligand
Authors: Pohl Siegfried , Bierbach Ulrich
Published: March 2015

The reaction of [Fe4S4I2(SC(NMe2)2)2] with racemic trans-1,2-bis(3-methylthioureido)-cyclohexane in tetrahydrofuran (thf) yields [Fe4S4I2(C6H10(NHCSNHMe)2)] · 4 thf (2). 2 crystallizes in the monoclinic space group C 2/c with a = 1471.7(2), b = 1329.7(2), c = 2339.3(3) pm, β = 107.70(1), V = 4362.3 × 106 pm3, Z = 4, R = 0.057. The cluster exhibits C2 symmetry in the solid state. The replacement of the monodentate neutral ligands results in a cluster in which the bifunctional thiourea derivative bridges two different iron sites of the slightly compressed [Fe4S4] core. The most striking feature are the differences of the Fe–Fe distances which are 269.8 pm between thiourea coordinated atoms and 280.7 pm between Fe atoms with iodide ligation. The Fe–S thiourea distance was found to be 229.3 pm.
Nitridocuprate(I): Quaternäre Phasen in den Systemen Li—Ca/Sr—Cu—N / Nitridocuprates(I): Quaternary Phases in the Systems Li—Ca/Sr—Cu—N
Authors: Jäger Jürgen , Kniep Rüdiger
Published: March 2015

The crystal structures of the intermediate phases in the quaternary systems Li–Ca/Sr–Cu–N are characterized by structural units containing substitutional positions (Li1-xCux) in two-fold and linear coordination by nitrogen. The bond-lengths (Li1-xCu1-x)–N are shortened with increasing Cu-content.

SrLi2[(Li1-xCux)N]2: Isotype of Li4SrN2; 0 ≦ x ≦ 0.39 (I 41/amd; Z = 4; x = 0.39: a = 377.0(1) pm, c = 2736.8(6) pm). (Li0.61Cu0.39)–N: 188.5(3) pm.

Sr[(Li1-xCux)N]: Isotype of Ba[NiN]; 0.33 ≦ x ≦ 0.52 (Pnma; Z = 12; x = 0.52: a = 900.1(3) pm, b = 1315.1(5) pm, c = 546.4(1) pm). (Li0.42Cu0.58)–N: 189.0(13) pm.

Ca2{(Li1-xCux)(a)[(Li1-xCux)(b)N2]}: Isotype of Sr2{Li[CoN2]}; 0.03 ≦ x(a) ≦ 0.27, 0.72 ≦ x(b) ≦ 0.80 (P42/mnm; Z = 2; x(a) = 0.27/x(b) = 0.80: a = 529.3(1) pm, c = 663.1(2) pm). (Li0.73Cu0.27)(a)—N: 188.0(7) pm; (Li0.20Cu0.80)(b)–N: 186.2(7) pm.

Based on the experimental results the bond-length CuI–N of two-fold (linear) coordinated Cu(I) in nitrido-compounds is estimated to be 184.5(5) pm.
Thermogravimetric Studies on Bimetallic Dithiocarbamate Complexes
Authors: Sodhi G. S. , Kaur J.
Published: March 2015

Thermogravimetric (TG) studies have been carried out for some bimetallic dithiocarbamate complexes of the type ZnML4 and NiM′L′4 [M = Co(II), Cu(II); M′ = Zn(II), Hg(II); L = N-methylcyclohexyldithiocarbamate; L′ = N-ethylcyclohexyldithiocarbamate]. From TG curves, the order, apparent activation energy and apparent activation entropy for the thermal decomposition reaction have been calculated. The thermal stabilities have been correlated with the structures of the complexes on the basis of hard and soft acid base (HSAB) theory.