bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis and Photodecomposition of Two Azido Derivatives of PCB
Authors: Bründl Angelika , Clausen Ernst , Buff Klaus
Published: March 2015

Synthesis of the PCB derivatives 4-azido-2,2′,4′,5,5′-pentachlorobiphenyl and 4,4′-diazido-2,2′,5,5′-tetrachlorobiphenyl is described. The compounds are easily photoactivated by UV-C irradiation. Thus these derivatives are valuable photolabels which have been used already in studies of intracellular distribution.
Notizen: Kristallstruktur von [As(C6H5)4]2[Re3Cl11(H20)] · H2O / Crystal Structure of [As(C6H5)4]2[Re3Cl11(H2O)] · H2O
Authors: Jung Bernd , Meyer Gerd
Published: March 2015

The crystal structure of

(AsPh4)2[Re3Cl„(H2O)]·H2O, previously thought to be (AsPh4)2[Re3Cl11], was redetermined from single-crystal four-circle diffractometer data. The crystal system is triclinic, PĪ, a = 983.1(6), b = 1200.5(6), c = 2566.2(10) pm, α = 92.67(4), β = 99.95(4), γ = 113.38(2)°, Vm = 817.95(1) cm3/mol, R = 0.043,Rw= 0.033.
Notizen: Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXVII [1] / Fluktuierendes Verhalten von Tris(Ether-Phosphan)-Ruthenium(II)-Komplexen / Novel Basic Ligands for the Homogenous Catalytic Carbonylation of Methanol, XXVII. Fluxional Behaviour of Tris(ether-phosphane) Ruthenium(II) Complexes
Authors: Lindner Ekkehard , Karle Berthold
Published: March 2015

Three equivalents of the ether-phosphane ligands 2a-c react with Cl2Ru(PPh3)3 (1) to give the complexes trans-Cl2Ru(P ̑O)(P∼O)2 (3a-c) (P∼O = η1-P-coordinated; P ̑O = η2-Ο,Ρ-coordinated). The hemilabile character of the P,O–ligands is becoming evident by the fluxional behaviour of 3 a-c. The coalescence temperatures in the AB part of their 31P{1H} NMR spectra are found at -10, 15 and -15 °C (AG* = 48, 53 and 47 kJ/mol). Because of steric effects, 3 a, in which the ether oxygen atom has the lowest basicity, and 3c, with the smallest ether substituent, show nearly the same dynamic properties.
Acetylenkomplexe von Rhenium(+ VI). Die Kristallstrukturen von [ReCl4(n-C3H7 – C= C – n-C3H7)(POCl3)] und ReCl4(THF)2 / Alkyne Complexes of Rhenium(+VI). The Crystal Structures of [ReCl4(n-C3H7 – C= C – n-C3H7)(POCl3)] and ReCl4(THF)2
Authors: Swidersky Hans-Walter , Pebler Jürgen , Dehnicke Kurt , Fenske Dieter
Published: March 2015

The results of the magnetic susceptibility measurements of the previously reported rhenium alkyne complexes [ReCl4(PhC≡CPh)]2.2 CH2Cl2 and [ReCl4(PhC=CPh)(CH3CN)] in the temperature range of 4.2-293 K suggest d1-configurations, corresponding with oxidation state +VI for the rhenium atoms. The new alkyne complex [ReCl4(n-C3H7–C=C–n-C3H7)(POCl3)] has been prepared by the reaction of ReCl5·OPCl3 with n-C3H7-C≡C–n-C3H7 in CCl4 solution, forming dark red single crystals, which were characterized by IR spectroscopy as well as by a crystal structure determination with X-ray methods (space group P2,/c, Z = 4, 3235 observed unique reflexions, R = 0.026; lattice dimensions at –70 °C: a = 805.6(2), b = 1000.6(4), c = 2188.8(6) pm, β = 79.59(2)°). [ReCl4(n-C3H7-C=C–n-C3H7)(POCl3)] has a molecular structure with the alkyne ligand bonded side-on (bond lengths Re-C 198.4 and 198.2(5) pm). The oxygen atom of the solvating POCl3 molecule is coordinated in trans position to the ReC2 unit of the alkyne ligand (bond length Re—O = 223.7(3) pm).

In THF solutions the alkyne complexes of this type undergo a slow reaction forming ReCl4(THF)2, which was also characterized by IR spectroscopy and a crystal structure determination (space group P212121, Z = 4, 2243 observed unique reflexions, R = 0.053; lattice dimensions at –70 °C: a = 773.0(14), b = 1267.1(6), c = 1398.6(7) pm). In ReCl4(THF)2 the THF molecules coordinate in cis-position (bond lengths Re–O 208 and 212(1) pm).
Darstellung, Eigenschaften und Kristallstruktur von [Diaqua-1,6-bis(benzimidazol-2-yl)-2,5-dithiahexan-nickel(II)]dibromid-Dihydrat / Synthesis, Properties and Molecular Structure of [Diaqua-1,6-bis(benzimidazol-2-yl)-2,5-dithiahexane-nickel(I I)]dibromide Dihydrate
Authors: Castiñeiras A. , Hiller W. , Strähle J. , Carballo R. , Bermejo M. R. , Gayoso M.
Published: March 2015

The synthesis, crystal structure and some spectroscopic properties of [Ni(BBDH)(OH2)2]Br2.2 H2O, (BBDH = 1,6-bis(benzimidazol-2-yl)-2,5-dithiahexane), are reported. The compound is obtained from nickel bromide hydrate and BBDH in ethanol. It crystallizes in the triclinic space group P 1̄ with a = 1155.5(3), b = 1203.9(2), c = 1047.0(2) pm, α = 111.62(4), β = 114.25(2), γ = 86.74(3)°, and Z = 2. The structure consists of [Ni(BBDH)(OH2)2]2+ cations joined through hydrogen bonding to two Br- ions and two molecules water of crystallization. BBDH is bound to the Ni2+
ion as quadridentate ligand with two N atoms of the two imidazole moieties in axial positions and the two S atoms in equatorial arrangement. The sixfold coordination is completed by two water molecules in trans-position to the S atoms. Raman, IR and mass spectra are discussed.
The Retention of Six-, Seven-, Eight-, and Twelve-Membered Ring Molecules of Type SexS y in Reversed-Phase HPLC. Prediction of Retention for Unknown SexS y Heterocycles and Analysis of Sulfur-Selenium Melts
Authors: Steudel Ralf , Strauss Eva-Maria , Jensen Detlef
Published: March 2015

The HPLC retention times of 25 cyclic compounds of type SexSy, (x = 0 · · · 8; y = 0 · · · 12) have been measured under identical conditions and are used to evaluate the factors which determine the retention. Linear relationships are derived for the dependence of retention (Ink'; k′ = capacity factor) on ring size, number of Se atoms, and number of SeS bonds per molecule for six-, seven-, eight-, and twelve-membered SexSy rings. These relationships allow the prediction of retention times for all SexSy heterocycles of these ring sizes (ca. 100 compounds). The results are applied to the qualitative analysis of mixed sulfur-selenium melts of two compositions: at a molar ratio of S : Se = 8.7 twenty-one HPLC signals have been observed for the CS2 extract of the quenched melt and assigned to SexSy rings of sizes 6··· 12. At S : Se = 0.33 mainly six-, seven-, and eight-membered species with cumulated Se atoms have been found.
Zur Reaktion von [Cp'2TiCl2] und [Cp TiCl3] mit E(SiMe3)2 (E = Se, Te; Cp' = C5H4CH3 / On the Reaction of [Cp'2TiC2] and [Cp′TiCl3] with E(SiMe3)2 (E = Se, Te; Cp′ = C5H4CH3)
Authors: Fenske Dieter , Grissinger Alfred
Published: March 2015

The complexes [Cp'4Ti2Te4] (1) (Cp′ = C5H4CH3) and [Cp′5Ti5EJ (E = Se :2, E = Te :3) have been prepared by the reaction of [Cp'2TiCl2] and [Cp′TiCl3] with E(SiMe3)2 (E = Se, Te). The structure of 1 consists of discrete [Cp′4Ti2Te4] molecules with the Ti2Te4 ring in the chair conformation. The crystal structure determinations of 2 and 3 show distorted Ti5 trigonal bipyramids with Se (2) or Te (3) as μ3 ligands.
Diisophorone and Related Compounds, Part 27 [1] Nucleophilic Reactions of 1-Halogenodiisophoranes
Authors: Kurzer Frederick , Duffner C. Richard
Published: March 2015

The action of nucleophiles on 1-halogenodiisophoranes, obtained by several methods from the corresponding 1-hydroxy or 1-alkoxy compounds, replaces their bridgehead 1-halogen by hydroxy, alkoxy or acetoxy groups. The semiquantitative results show that the high solvolysis and hydrolysis rates of the 1-halogenodiisophor-2(7)-en-3-ones contrast markedly with the low reactivities of their 3-deketo analogues. Perchloric acid-catalyzed acetylation of diisophor-2(7)-en-1-ol-3-ones yields, by enolisation of the 3-keto-group, 1,3-diacetoxydiisophora-2,7-dienes in addition to the usual 1-monoacetates.
K{μ-Cl2Al[CH(SiMe3)2]2} – Kristallstruktur eines eindimensional über K – Cl-Brücken koordinationspolymeren Alanats / K{µ-Cl2Al[CH(SiMe3)2]2} – Crystal Structure of an Alanate Featuring a Onedimensional Coordination Polymer with K–Cl Bridges
Authors: Uhl Werner
Published: March 2015

The title compound is formed as a by-product in the synthesis of tetrakis[bis(trimethylsilyl)methyl]dialane(4) from potassium and chloro-bis[bis(trimethylsilyl)methyl]alane or by addition of KCl to the starting alane. 1 is a monomer in benzene solution, but a polymer in the solid state with chains formed via potassium-chlorine bridges. An interaction between a C-H σ-bond of one trimethylsilyl group and each potassium ion has also been detected
Zur Existenz schwacher Wechselwirkungen zwischen Sb(III) und Phenylgruppen: Sb2Br6(SPPh3)2, Sb2I6(SePPh3)2 · 2 CH2Cl2, Sb4Br12(SPMe2Ph)4 und (Ph4P)2Sb2Br8 · CH3CN / On the Existence of Weak Interactions between Sb(III) and Phenyl Groups: Sb,Br6(SPPh3)2, Sb2I6(SePPh3)2 · 2CH2Cl2, Sb4Br12(SPMe2Ph)4 and (Ph4P)2Sb2Br8 · CH3CN
Authors: Pohl Siegfried , Saak Wolfgang , Lotz Rainer , Haase Detlev
Published: March 2015

The compounds Sb2Br6(SPPh3)2 (1), Sb2I6(SePPh3)2·2CH2Cl2 (2), and Sb4Br12(SPMe2Ph)4 (3) were prepared in nearly quantitative yield by reacting of SbBr3 or SbI3 with the corresponding thio- or selenophosphoranes in dichloromethane solution. The reaction of SbBr3 and Ph4PBr in acetonitrile solution yields (Ph4P)2Sb2Br8 · CH3CN (4). The crystal structures of compounds 1-4 were determined from single crystal X-ray diffraction data.

1: monoclinic, space group P21/n with a = 875.3(1), b = 1366.0(1), c = 1837.0(1) pm, β = 100.28(1)°, V = 2161.1 × 106 pm3 and Z =2.

2: monoclinic, P21/n, a = 1021.6(4), b = 1285.7(4), c = 2088.8(6) pm, β = 96.45(3)°, V = 2726.4 × 106 pm3, Z = 2.

3: monoclinic, P21/n, a = 1180.5(1), b = 1407.9(1), c = 1891.5(2) pm, β = 106.35(2)°, V = 3016.6 × 106 pm3, Z = 2.

4: monoclinic, C 2/c, a = 2213.1(2), b = 1387.5(1), c = 1955.6(1) pm, β = 112.33(1)°, V = 5523.2 × 106 pm3, Z = 4.

1,2 and the anion of 4 contain centrosymmetric dimeric units with bridging halogen atoms. In all three compounds weak interactions between antimony and phenyl groups complete the sixfold coordination of Sb(III) (Sb-C: 339-365 pm). The crystal structure of 3, however, exhibits tetramers [SbBr3(SPMe2,Ph)]4 with bridging halogen and sulfur atoms, and without Sb-phenyl contacts. The conclusion from the different structures is that there is only a minor structural influence of the observed weak interactions
Notizen: Marginalin, a Substance from the Pygidial Glands of Dytiscus Marginalis (Coleoptera): Molecular Associations with Polyamines in vitro
Authors: Barbier Michel
Published: March 2015

Marginalin, a product previously isolated from the pygidial glands of the water-beetle Dytiscus marginalis (Coleoptera), strongly reacts in vitro to form complexes with polyamines of biological interest. With spermin and spermidin, this interaction is specific giving 1:1 complexes which were isolated and studied (physico-chemical data). The results so far observed are discussed in relationship with the known biological properties of spermin and spermidin and the significance of marginalin in the defensive secretion of the beetle
Synthesis and Structure of 1,2,3-Tritellura-[3]ferrocenophane
Authors: Herberhold Max , Leitner Peter , Thewalt Ulf
Published: March 2015

The missing tellurium member of the 1,2,3-trichalcogena-[3]ferrocenophanes, Fe(C5H4Te)2Te, was synthesized and structurally characterized. The shiny needles are composed of alternating layers of tellurium and parallel ferrocene units. The molecules Fe(C5H4Te)2Te contain eclipsed cyclopentadienyl rings which are connected by a Te3 bridge.
Lithium-Iminofluorsilan und Natriumfluorsilylamid – ein Vergleich / Lithium-Iminofluorosilane and Sodium-Fluorosilylamide – a Comparison
Authors: Stalke Dietmar , Pieper Ursula , Vollbrecht Susanne , Klingebiel Uwe
Published: March 2015

The metalation of 2,4,6-tri-tert-butylamino-tert-butylfluoromethylsilane (1) with butyllithium leads to the formation of the LiF adduct of the iminosilane 2. In 2 the silicon atom is pentavalent and four-coordinated. The corresponding sodium compound is the fluorosilylamide 3. The nitrogen has a planar environment in 3.
Zur Umsetzung von Tri(phenylethinyl)arsan und -stiban mit Octacarbonyldicobalt; Kristallstruktur von (Ph– C≡ C)As[(η2-C≡ C – Ph)Co2(CO)6]2 / Reaction of Tri(phenylethynyl)arsane and -stibane with Octacarbonyldicobalt; Crystal Structure of (Ph–C≡C)As[η2-C≡C–Ph)Co2(CO)6]2
Authors: Lang Heinrich , Zsolnai Laszlo
Published: March 2015

The synthesis of tri(phenylethynyl)arsane (1) and -stibane (7) is discussed. Octacarbonyldicobalt reacts selectively with 1 or 7 to yield the η2-side-on co-ordinated phenylethynyl complexes (Ph–C=C)nE[(η2-C≡C–Ph)Co2(CO)6]3-n (E = As: n = 2: 3, n = 1: 4, n = 0: 5; E = Sb: n = 2: 8; n = 1: 9; n = 0: 10), which contain sterically hindered carbon-cobalt tetrahedrane cluster units. 3 gives upon heating {(Ph–C≡C)2As[(η2-C=C–Ph)Co2(CO)5]}2 (6) a compound containing a six-membered Co2As2C2 ring.

All new compounds have been characterized by analytical and spectroscopic data (IR, 1H, 13C NMR), and (Ph –C≡C)As[(η2-C≡C–Ph)Co2(CO)6]2 (4) by X-ray analysis.
Kristallstruktur des Li2MnCl4 / The Crystal Structure of Li2MnCl4
Authors: Lutz Heinz Dieter , Schneider Michael
Published: March 2015

The crystal structure of the spinel type fast ionic conductor Li2MnCl4 is redetermined by single crystal X-ray diffraction with respect to both cation distribution and Frenkel disorder. The final R value for 166 unique reflections is 0.029 (space group Fd3m, structural parameter u = 0.25623(3), a = 1050.27(5) pm). Contrary to the results based on neutron powder data (van Loon and de Jong, 1975) Li2MnCl4 is fully inverse. The thermal ellipsoids of the ions involved are discussed in terms of the lattice vibrations of the spinel structure and the mobility of the lithium ions.
Synthese, Struktur und Reaktivität labiler Rhodium(I)-Komplexe mit iPr2PC2H4NMe2 und iPr2PC2H4OMe als Phosphanliganden / Synthesis, Structure and Reactivity of Labile Rhodium(I) Complexes Containing iPr2PC2H4NMe2 and iPr2PC2H4OMe as Phosphine Ligands
Authors: Werner Helmut , Hampp Andreas , Peters Karl , Peters Eva Maria , Walz Leonhard , Schnering Hans Georg von
Published: March 2015

Square-planar rhodium(I) complexes [RhCl(iPr2PC2H4Y)2] (8, 9) containing one chelating and one P-bonded monodentate phosphine ligand are prepared from [RhCl(C8H14)2]2 (7) and the new functionalized phosphines iPr2PC2H4Y (5,6). Reaction of 9 (Y = NMe2) with CO and of 8 (Y = OMe) with CO, C2H4, C2H2, C2Ph2 and HC2Ph leads to opening of the chelate ring and formation of the complexes trans-[RhCl(L)(η1-P–iPr2PC2H4Y)2] (10-15). Treatment of 8 with H2 gives the dihydridorhodium(III) compound [RhH2Cl(iPr2PC2H4OMe)2] (16). The vinylidene complexes trans-[RhCl(=C=CHR)(η1-P– iPr2PC2H4OMe)2] (17, 18) are obtained by thermal or pyridine promoted rearrangement of 13 (L = C2H2) and 15 (L = HC2Ph). 13 and 15 have also been used as starting materials for the synthesis of the cyclopentadienyl alkyne and vinylidene complexes 19-21. The X-ray crystal structure of the parent compound 8 was determined.
Aminosubstituierte Organoindiumchloride: [i-Pr(Cl)InN(H)t-Bu]2 und [Mes(Cl)InN(SiMe3)2]2 / Amino-Substituted Organoindium Chlorides: [i-Pr(Cl)InN(H)t-Bu]2 and [Mes(Cl)InN(SiMe3)2]2
Authors: Neumüller Bernhard
Published: March 2015

The reactions of isopropyl indium dichloride (1) with LiN(H)t-Bu and of mesityl indium chloride (2) with NaN(SiMe3)2 lead to compounds [i-Pr(Cl)InN(H)t-Bu]2 (3) and [Mes(Cl)InN(SiMe3)2]2 (4), respectively. 3 forms dimers in solution and in the solid state, while the monomer is the predominate species of 4 in solution. 3 crystallizes in 2 isomers. The X-ray analysis of one isomer of 3 is reported.
Heterocyclische Siebenring-Verbindungen, XXXVII. Synthese und thermische Umlagerung von 1-Methyl- l -benzothiepinium-tetrafluoroborat / Heterocyclic Seven-Membered Ring Compounds, XXXVII. Synthesis and Thermal Rearrangement of 1 -Methyl-1-benzothiepinium Tetrafluoroborate
Authors: Hofmann Hans , Fischer Herbert , Vries Markus de
Published: March 2015

Reaction of 1-benzothiepine (4), whose synthesis has been improved, with trimethyloxonium tetrafluoroborate yields 1-methyl-1-benzothiepinium tetrafluoroborate (5). Compound 5 rearranges to methyl 1-naphthyl sulfide (6) on heating in acetonitrile. The reaction rate 5 → 6 was determined at one temperature (75°C).
Notizen: Darstellung und Struktur des Addukts (η5-C5Me5)TaF4· HN =PPh3 / Preparation and Structure of the Adduct (η5-C5Me5)TaF4 · HN = PPh3
Authors: Schrumpf Frank , Roesky Herbert W. , Noltemeyer Mathias
Published: March 2015

Cp*TaF4 (1) (Cp* = η5-C5Me5) forms a Lewis acid Lewis base adduct with the iminophosphorane HN = PPh3 (2). The adduct Cp*TaF4·NH=PPh3 (3) is remarkably stable to thermal decomposition. The X-ray crystal structure of 3 was investigated.
Notizen: A New Pentaoxygenated Xanthone from the Fern Cystopteris fragilis
Authors: Imperato Filippo
Published: March 2015

A new pentaoxigenated xanthone has been isolated from aerial parts of the fern Cystopteris fragilis. By spectroscopic and chemical methods this compound has been shown to be 1,6-dihydroxy-3,5,7-trimethoxyxanthone which is of biosynthetic interest in ferns.
Synthese und Kristallstruktur von Te4
2+(MoOCl4)2
2- / Synthesis and Crystal Structure of Te4
2+(MoOCl4)2
2-
Authors: Beck Johannes
Published: March 2015

MoOCl4 reacts with two equivalents of tellurium in a sealed evacuated ampoule at 250 C to give Te4
2+(MoOCl4)2
2- in quantitative yield. Te4(MoOCl4)2 forms black crystals which rapidly decompose in moist air. The crystal structure determination (lattice constants a = 1192.9(3), b = 683.7(2), c= 1049.8(2) pm, β = 90.08(2) , Ζ = 2, monoclinic space group P21/n, 1907 unique reflections for 73 parameters, final R = 0.013) shows, that Te4(MoOCl4)2 consists of nearly ideal square Te4
2+ cations with Te–Te distances of 269.1 and 269.9 pm and dimeric (MoOCl4)2
2- anions, in which Mo atoms are linked by asymmetric chloro bridges (Mo–Cl = 278.3 and 241.0 pm). The oxygen ligand (Mo–O = 164.7 pm) is located in the trans position to the longer Mo–Cl bond. Close contacts as short as 315.8 pm between chlorine and oxygen to the cation show considerable anion-cation charge-transfer interaction.
Heterocycles Synthesis through Reactions of Nucleophiles with Acrylonitriles, Part 9. A Direct One-Pot Synthesis of Pyranopyrazoles
Authors: Abdel-Latif Fathy Fahim
Published: March 2015

Several pyrano[2,3-c]pyrazoles were synthesized through a convenient one-pot method in excellent yields. Structure and reaction pathways are also reported and supported by another synthetic route.
Tetramethylpyrrolyl-Phosphane / Tetramethylpyrrolyl Phosphanes
Authors: Kuhn Norbert , Jendral Kai
Published: March 2015

The 2,3,4,5-tetramethylpyrrolyl phosphanes (pyr)nPCl3-n(2-4, pyr = C4Me4N; n = 1-3) are obtained by the reaction of PCl3 with lithiated 2,3,4,5-tetramethylpyrrole 1, 2 and 3 react with Mg to give the cyclotetraphosphane (pyrP)4 7 and the diphosphane pyr2P—Ppyr2 8, respectively. Spectroscopic and chemical properties indicate the pyrrolyl ligand to be co-ordinated by a single P—N bond not essentially influenced by π-bonding.
Vollständige Maskierung der –Gly-Bindungen mit dem stark lipophilen und chromophoren Ferrocenylmethyl[Fem]-Rest bei Peptidsynthesen von Hexaglycin und Leu-Enkephalin / Total Masking –Gly Bonds by Highly Lipophilic and Chromophoric Ferrocenylmethyl [Fem] Residue in Peptide Syntheses of Hexaglycine and Leu-Enkephalin
Authors: Eckert Heiner , Forster Barbara , Seidel Christoph
Published: March 2015

Highly lipophilic and chromophoric ferrocenylmethyl [Fem] residue is applied to syntheses of peptides hexaglycine and Leu-enkephalin, masking therein all –Gly bonds. Thereby Fem groups influence properties of Fem-peptide derivatives advantageously both in chemosyntheses and cleaning operations, leading to constantly high yields et each step. Despite of its volumous dimension the Fem residue can be introduced into each peptide bond of oligoglycine by succeeding one another of building blocks of H–Fem–Gly–OMe. Strong alkaline conditions during the hydrolyses of methyl esters occurring several times in peptide derivatives do not influence the Gly–Gly-bond at all. Total protected derivatives BOC–(Fem–Gly–)6OMe and BOC–Tyr(tBu)–(Fem–Gly–)2Phe–Leu–OtBu even are soluble in hexane/ethylacetate (1:1).
Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXXI Kationische Bis(Ether-Phosphan)metall-Komplexe der Nickeltriade mit fluktuierendem Verhalten / Novel Basic Ligands for the Homogeneous Catalytic Methanol Carbonylation, XXXI Cationic Bis(Ether-Phosphine)Metal Complexes of the Nickel Triad with Fluxional Behavior
Authors: Lindner Ekkehard , Dettinger Johannes
Published: March 2015

The (ether-phosphine) ligands R2PCH2C5H9O (1a-c) [R = Ph (a), Cy (= cyclo-C6H11) (b), n-C3H7 (c); C5H9O = tetrahydropyranyl] are obtained from the corresponding alkali metal phosphides MPR2 (M = Li, Na) and 2-chloromethyltetrahydropyran in ether. Reaction of 1 a-c with either Cl2M(COD) (COD = 1,5-cyclooctadiene) or [Ni(OH2)6]Cl2 in a2:1 ratio leads to the bis(ether-phosphine)metal complexes Cl2M(R2P∾O)2 trans-2b,c, trans-3b, cis-2a,b, cis-3a, and 4a [M = Pd (2), Pt (3), Ni (4)], in which the ligands 1a-c are η1-P-coordinated. In 2—4 Cl- is abstracted by AgClO4 to give the cationic trans-bis(ether-phosphine) complexes [ClM(R2P ∾ O)(R2P~O)][ClO4] (5a, 6a-c, 7a) [M = Ni (5), Pd (6), Pt (7); P∾O = η1-P-coordinated; P~O = η2-O,P-coordinated]. In contrast to 7a, the nickel and palladium complexes 5a and 6a-c show fluxional behavior as demonstrated by temperature dependent 31P{1H} NMR spectra. The coalescence temperatures and estimated free energie enthalpies ΔG≉ of 5a and 6a-c are compared with the corresponding data of the complexes [ClPd(Ph2P ∾ O)(Ph2~O)][ClO4] (8a-10a) [O,P ligand = Ph2PCH2C4H7O (8a), Ph2PCH2C4H7O2 (9a), Ph2PCH2CH2OCH3 (10a)] and give an insight into the relative basicity of the ether oxygen atoms.
Zinkkomplexe des Liganden Tris(methylaminomethyl)-ethan / Zinc Complexes of the Ligand Tris(methylaminomethyl)ethane
Authors: Brandt Willi , Wirbser Joachim , Powell Anne K. , Vahrenkamp Heinrich
Published: March 2015

The title ligand CH3C(CH2—NHCH3)3 was used to prepare complexes with zinc salts. In addition to the known 1:1 complexes of ZnCl2 and ZnBr2, those of ZnI2, Zn(SCN)2, Zn(CH3COO)2, and Zn(NO3)2, and the bis-ligand complex of Zn(ClO4)2 were obtained and characterized. Crystal structure determinations revealed a tetrahedral coordination with two nitrogen atoms of the ligand and two anions bound to zinc for the acetate complex and for the thiocyanate complex, upon crystallization of which the ligand was converted to an acetone aminal. In the bis-ligand zinc perchlorate complex the ligand is tridentate, and zinc has an octahedral coordination.
Crystal Structure of a Diazenido-Dithiocarbamate Complex of Technetium, [Tc(NNC6H4Cl)((CH3)2NCS2)2(PPh3)]
Authors: Dilworth Jon R. , Jobanputra Panna , Thompson Russell M. , Archer Colin M. , Kelly J. Duncan , Hiller Wolfgang
Published: March 2015

The title complex [Tc(NNC6H4Cl)((CH3)2NCS2)2(PPh3)] crystallizes in the monoclinic space group C 2/c with a = 3305.6(2), b = 1155.3(1), c = 2545.1(2) pm and β = 131.065(5)°. The final R value is 0.044.
Methylzinn- und Methylindium-bis(trimethylsilyl)amide / Methyltin and Methylindium Bis(trimethylsilyl)amides
Authors: Rannenberg Michael , Weidlein Johann , Obermeyer Axel
Published: March 2015

BrSn[N(SiMe3)2]3 and ClIn[N(SiMe3)2]2 react with LiMe · O(C2H5)2 (Me = CH3) in toluene or hexane to give the corresponding amido derivatives MeM[N(SiMe3)2]x (M = Sn, x = 3 and M = In, x = 2). These new compounds and the other members of the homologous series MenM[N(SiMe3)2]4 or 3-n are characterized by their IR, Raman und NMR spectra. In addition, the results of the crystal structure determination of MeSn[N(SiMe3)2]3 are reported.
Heteronukleare Komplexverbindungen mit Metall–Metall-Bindungen, V [1] / Heteronuclear Co-ordination Compounds with Metal–Metal-Bonds, V [1]
Authors: Fuchs Ralf , Klüfers Peter
Published: March 2015

The heteronuclear carbonyl complex [(NH3)2CuCo(CO)4] 1 reacts with the phosphane ligands PPh3, PEt3 and P(OMe)3. A dinuclear complex, [(PPh3),CuCo(CO)4] 2, is formed with PPh3, while trinuclear anionic [Cu{Co(CO)4}2]- species are formed with the other phosphane ligands. The crystal structure of 2 (Cu—Co = 255.2(2) pm) and the structures of two compounds with trinuclear anions, [Cu{P(OMe)3}4][Cu{Co(CO)4}2] 3 (Cu—Co = 232.64(8) and 233.10(8) pm) and PPN[Cu{Co(CO)4}2] 6 (Cu—Co = 238.1(1) and 234.3(1) pm), have been determined by X-ray crystallography. The angle Cax—Co—Ceq of tetracarbonyl cobalt compounds (i. e. the deviation from tetrahedral geometry) depends on the charge of the Co(CO)4 fragment, as calculated with the electronegativity equalization scheme of Bratsch (J. Chem. Ed. 61, 588 (1984)).
EPR- und ENDOR-Untersuchungen von Benzo[c]phenanthrensemichinonen / EPR and ENDOR Investigations of Benzo[c]phenanthrene Semiquinones
Authors: Maurer Manfred , Stegmann Hartmut B. , Andert Doris , Mannschreck Albrecht
Published: March 2015

A series of benzo[c]phenanthrene semiquinone diphenylthallium complexes was prepared in pyridine from the corresponding quinones. EPR, ENDOR and TRIPLE spectra provided the proton coupling constants and, in most cases, their assignments and their relative signs. The thallium splittings are discussed in terms of the extent of the twist in the semiquinones and solvation of the complexes.
M(IV)–M′(O)-Zweikernkomplexe (M = Ti, Zr, M′ = Cr, Mo, W) mit verbrückenden Phosphinocyclopentadienid-, Chlorid- und Thiolatliganden / M(IV)–M′(O) Dinuclear Complexes (M = Ti, Zr, M′ = Cr, Mo, W) with Bridging Phosphinocyclopentadienide, Chloride, and Thiolate Ligands
Authors: Schenk Wolfdieter A. , Neuland-Labude Christine
Published: March 2015

A series of ligand-bridged dinuclear complexes [MM′Cl(µ-Cl)(µ-C5H4PR2)2(CO)3] (M = Ti, Zr, M′ = Cr, Mo, W, R = C6H5, 4-C6H4CH3) was synthesized from the mononuclear precursors MCl2(C5H4PR2)2 and M′(CO)3L3. Donor ligands L cleave the chloro bridge either reversibly (L = acetonitrile) or irreversibly (L = CO, P(OMe)3) with formation of the adducts [MM′Cl2(μ-C5H4PR2)2(CO)3L]. At titanium a terminal Cl- ligand can be replaced by tBuO- whereas MeS- substitutes both terminal and bridging Cl-. The dinuclear complexes [MM′(SMe)(µ-SMe)(µ-C5H4PR2)2(CO)3] thus formed are inert towards CO or P(OMe)3.
Crystal Structure of K[CpFe(CO)2]: Helical Chains with Strong Cation-Anion Interactions between the Helices
Authors: Hey-Hawkins Evamarie , Schnering Hans Georg von
Published: March 2015

The reaction of KSi with [CpFe(CO)2]2 in DME (1,2-dimethoxyethane) yields deep red crystalline K[CpFe(CO)2] (1). 1 crystallizes monoclinically in the space group P21/a (No. 14) with a = 10.953(4), b = 10.159(3), c = 7.347(2) Å, β = 107.89(2)°, Ζ = 4, R = 0.028, Rw = 0.030. Crystals of 1 consist of polymeric chains, formed by strong K-O interactions [d(K-O) 2.915(2), 2.773(2) A], while van-der-Waals interaction between neighboring helices leads to formation of a three-dimensional network with short distances d(K-C) [3.173(3) to 3.292(3) A].
Darstellung und Kristallstruktur von (Se4)2(Sb4F17)(SbF6)3 / Preparation and Crystal Structure of (Se4)2(Sb4F17)(SbF6)3
Authors: Minkwitz Rolf , Borrmann Horst , Nowicki Joachim
Published: March 2015

(Se4)2(Sb4F17)(SbF6)3 is formed by reaction of selenium with a large excess of SbF5 in SO2 at 363 K. It crystallizes in the monoclinic space group P21/n (Nr. 14) with a = 1124.1(2), b = 1342.7(2), c = 1151.2(3) pm; β = 93.10(2)° and Z = 2. Two crystallographically independent Se4
2+ units exhibit slight differences of bond distances and angles as well as different numbers of cation-anion interactions. Three regular SbF6
- octahedra and the mixed valent Sb4F17
- anion, observed previously in only one case, are present.
Übergangsmetallkomplexe mit Schwefelliganden, LX / Transition Metal Complexes with Sulfur Ligands, LX
Authors: Sellmann Dieter , Höhn Klaus , Moll Matthias
Published: March 2015

The pentadentate thioether thiolate ligand ′buS5′2 (= dianion of 2,2′-bis(2-mercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) reacts with iron(II) ions to give the diamagnetic [Fe′buS5′] (1), which only coordinates σ-π ligands such as CO, NO, NO+ or P(OPh)3. In this respect, the [Fe′buS5′] fragment differs from the parent complex [Fe′S5′] (′S5′2
- = dianion of 2,2′-bis(2-mercaptophenylthio)diethylsulfide) as well as from the related [Fe′NHS4′] (′NHS4′2- = dianion of 2,2′-bis(2-mercaptophenylthio)diethylamine), both of which are able to coordinate also σ-ligands such as N,H4 or NH3. Synthesis of [Fe(CO)′buS5′] (2), yields two stereoisomers that can be easily separated owing to their different solubility.
Reversible Öffnung von Metall-Metall-Bindungen: Quantitative Untersuchung des Ringöffnungsgleichgewichts von [Cp′(CO)2Mn]2SeAryl+ / Reversible Opening of Metal Metal Bonds: Quantitative Analysis of the Ring Opening Equilibrium for [Cp′(CO)2Mn]2SeAry1+
Authors: Lau Patrizia , Huttner Gottfried , Zsolnai Laszlo
Published: March 2015

The compounds [Cp′(CO)2Mn]2SeR+ are isoelectronic analogues of the well known “inidene”-species [LnM]ER (E = P, As, Sb, Bi). While these latter “inidene” compounds exist in an open form with no metal-metal-interaction and the main group atom in a trigonal planar environment allowing for a three-center-4π-system M

E

M, their isoelectronic selenium analogues generally show equilibria between the “inidene”-type metal metal non bonded forms and their metal metal bond closed cyclic isomers. In a valence bond picture the four electrons, delocalized in the three-center-4π-system of the open isomers, are localized in the closed ones: two in the metal metal bond and two as a lone pair at a pyramidally coordinated selenium center.

The corresponding equilibria are quantitatively analyzed for [Cp′(CO)2Mn]2SeR+ (R =

PCF3-C6H4 (1), PCH3-C6H4 (PToI) (2), °CH3—C6H4 (°Tol) (3)) by UV/VIS spectroscopy of their solutions at different temperatures. The ring opening process which corresponds to the reversible opening of a metal metal bond is found to be entropically driven with reaction-entropies of around 25 [JΚ-1mol-1]. Correspondingly, imposing steric hindrance on R, [Cp′(CO)2Mn]2SeMes+ (4) yields a stable bond opened “inidene”-type compound. Reducing steric hindrance in [Cp′(CO)2Mn]2Se′Pr+ (5) gives the bond closed form as the only detectable isomer.
Complexes of Zn, Cd and Hg Halides with S and N Polydentate Schiff-Base. Metal Template Effect in the Synthesis of Analogous Oxygenated Base. Crystal Structure of [Zn(btsc)2Cl2] and [Cd(btsc)2Br2]
Authors: Souza Pilar , Sanz Luisa , Fernández Vicente , Arquero Agueda , Gutierrez Enrique , Monge Angeles
Published: March 2015

Zinc, cadmiun and mercury dihalide react with 4-acetylpyridinthiosemicarbazone (4-aptsc) to give complexes with 1:1 and 2:1 ligand/metal stoichiometric ratios. These metals are effective templates for the Schiff-base condensation of 4-acetylpyridine with semicarbazide to give the complexes [M(4-apsc)X2] and [M(4-apsc)2X2] where M = Zn, Cd or Hg and X = Cl, Br or I. These compounds were characterized by elemental analyses, conductivities measurements, IR and 13C, 1H NMR spectra.

The zinc chloride and bromide complexes of benzalthiosemicarbazone (btsc) have been prepared and characterized by X-ray measurements.

The compounds Zn(btsc)2Cl2 and Cd(btsc)2Br2 are isostructural and crystallize in the space group P21/n. The crystal structure of the chlorine derivative has been resolved by single-crystal X-ray diffraction. The zinc centre is in a slightly distorted tetrahedral environment. There are intra and intermolecular hydrogen bonds.
Synthese von Di- und Tri(o-phenylendiamin)-Liganden / Synthesis of Di- and Tri(o-phenylenediamine) Ligands
Authors: Ekkehardt Hahn F. , Dittler-Klingemann Andreas
Published: March 2015

The o-phenylenediamine ligand tris[3-(2,3-diaminophenoxy)propyl]amine, TRIPACEN (4) and bis[3-(2,3-diaminophenoxy)propyl]amine, DIPACEN (8) are obtained by Williamson coupling of the potassium salt of 2,3-dinitrophenole (1) to tris(3-chlorpropyl)amine (2) or benzylbis(3-chlorpropyl)amine (5), respectively, followed by reduction of the nitro functions with Sn/HCl or Pd(OH)2/H2.
Kristallstrukturen von [P(C6H5)4]2[B6Cl6](CH3CN)2 und [P(C6H5)4]2[B6Br6](CH3CN)2 sowie Schwingungsspektren und Normalkoordinatenanalyse der isotopomeren closo-Hexahalogenohexaborate [11Bn
10B6-nX6]2-, Χ = Cl, Br; n = 0-6 / Crystal Structures of [P(C6H5)4]2[B6Cl6](CH3CN)2 and [P(C6H5)4]2[B6Br6](CH3CN)2, Vibrational Spectra and Normal Coordinate Analysis of Isotopomeric closo-Hexahalogenohexaborates [11Bn
10B6-nX6]2-, X = Cl, Br; n = 0-6
Authors: Thesing J. , Baurmeister J. , Preetz W. , Thiery D. , Schnering H. G. von
Published: March 2015

The crystal structures of (TPP)2[B6Cl6](CH3CN)2 and (TPP)2[B6Br6](CH3CN)2 were determined from single crystal X-ray diffraction analyses at 147 K. They are triclinic, space group P1̅, and contain nearly regular octahedral anions with bond lengths d(B-B) 1.716, d(B-Cl) 1.818 for [B6Cl6]2- and d̅(B-B) 1.684, d̅(B-Br) 1.993 Å for [B6Br6]2-. Using these molecular data, normal coordinate analyses for the ten isotopomers [11Bn
10B6-nX6]2-, n = 0-6, X = Cl, Br, including the pairs of geometric isomers for n = 2, 3, 4 have been performed, based on a general valence force field. With a set of 8 force constants for Cs2[B6Br6] (e.g. fd(BB) = 1.39, fd(BBr) = 3.18 mdyn/Å) and 10 for Cs2[B6Cl16] (e. g. fd(BB) = 1.30, fd(BCl) = 4.01 mdyn/Å) the calculated frequencies are in good agreement with observed IR (10 K) and Raman bands (80 K) in natural abundance as well as for 11B- and 10B-enriched derivatives. For the series [B6X6]2-, X = Cl, Br, I the correlation of decreasing bond lengths d(B-B) and increasing force constants fd(BB) along with vibrational coupling between the B6 cage and the substituent sphere is discussed.
Pyridazine Derivatives and Related Compounds, Part 3 [1] Some Reactions with 4-Cyano-3(2H)-pyridazinethione
Authors: Deeb Ali , Essawy Abdel Naby , Yasine Fathy , Fikry Rida
Published: March 2015

The reaction of 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide 2 with formamide, acetic anhydride and carbon disulphide yielded pyrimido[4′,5′ :4,5]thieno[2,3-c]-pyridazin-4-one derivatives. Pyrimido[4,5-c]pyridazinethione and dithione derivatives were obtained by cyclocondensation of 3-amino-5,6-diphenylpyridazine-4-carbonitrile (8) with phenyl isothiocyanate and carbon disulphide, respectively. Tetrahydropyridazino[3,4-b]-quinoline (11) was prepared by reaction of 8 with cyclohexanone in presence of zinc chloride.
Oxidative Addition von Tetramethyldiphosphan und -arsan an Cp′–SiMe2–Cp′-überbrückte Molybdän- und Wolframcarbonyl-Komplexe / Oxidative Addition of Tetramethyldiphosphane and -arsane to Binuclear Cp′–SiMe2–Cp′-Bridged Molybdenum and Tungsten Carbonyl Complexes
Authors: Abriel Walter , Baum Gerhard , Burdorf Heike , Heck Jürgen
Published: March 2015

Thermal reaction of Me2Si[Cp′M(CO)3]2 (M = Mo, W; Cp′ = C5H4) with tetramethyldiphosphane and -diarsane gives oxidative coupling products with bridging EMe2-groups (E = P, As). With E = P discrete binuclear compounds are obtained, which on further thermolysis afford new species of the general formula {Me2Si(Cp′M)2(CO)3(μ-PMe2)2} (5). X-Ray structure determination of 5 a (M = Mo) and NMR data show a PMP-heteroallylic system which is bound to the second metal. In the case of M = W a second compound with a mixed hydrido and dimethylphosphido bridge can be isolated, which shows fluxionality in solution. However, the oxidative additions with tetramethyldiarsane lead to insoluble products which are assumed to be polymeric with Cp′–SiMe2–Cp′ as well as AsMe2 bridges linking the metal centers.
Darstellung und spektroskopische Charakterisierung von Methyltrifluormethyliodoniumhexafluorometallaten CH3ICF3
+MF6
- (M = As, Sb) / Preparation and Spectroscopic Characterization of Methyltrifluoromethyliodonium Hexafluorometallates CH3ICF3
+MF6
- (M = As, Sb)
Authors: Minkwitz Rolf , Gerhard Volker
Published: March 2015

The methyltrifluoromethyliodonium salts CH3ICF3
+MF6- are prepared by methylation of CF3I with CH3OSO+MF6- (M = As, Sb) in liquid SO2. The compounds have been characterized by Raman and NMR spectroscopy. Attempts to prepare the analogous bromonium compounds were not successful.
Gehinderte Ligandbewegungen in Übergangsmetallkomplexen, XXXVIII [1]. [4+5]-Cycloaddition von 2,3-Dimethyl-1,3-butadien an Tricarbonyl- η5-2,4-pentadienyl-mangan und Tricarbonyl-η5-dimethyl-2,4-pentadienyl-mangan / Hindered Ligand Motions in Transition Metal Complexes, XXXVIII [1]. [4+5] Cycloaddition of 2,3-Dimethyl-1,3-butadiene to Tricarbonyl(η5 -2 ,4 -pentadienyl)manganese and Tricarbonyl(η5 -2 ,4 -dimethyl-2 ,4 -pentadienyl)manganese
Authors: Kreiter Cornelius G. , Lehr Klaus , Heeb Gerhard
Published: March 2015

Tricarbonyl(η5-2,4-pentadienyl)manganese (1) and tricarbonyl(η5-2,4-dimethyl-2,4-pentadienyl)manganese (2) photochemically add 2,3-dimethyl-1,3-butadiene (3). Mediated by manganese, 6,7-dimethyl-2,6-cyclononadiene-1-yl and 1,3,6,7-tetramethyl-2,6-cyclononadiene-1-yl complexes are formed. Η-shifts from the methyl groups of the substituted CC double bonds convert the primary products into tricarbonyl-η3:CH-l-methylene-2-methyl-6-cyclononen-2-ylmanganese (4), and tricarbonyl-η3:CH-1-methylene-2,5,7-trimethyl-6-cyclononen-2-yl-manganese (6), respectively. In addition tetracarbonyl-η3-1-methylene-2-methyl-6-cyclononen-2-yl-manganese (5), and tetracarbonyl-η3-1-methylene-2,5,7-trimethyl-6-cyclononen-2-ylmanganese (7) are obtained. The latter are also formed from 4 and 6 by addition of CO under ambient conditions. In the complexes 4 and 6 the hydrocarbon ligands are coordinated by enyl units, encompassing C 1, C2, and the exocyclic methylene group, and by a C-H-Mn 2-electron-3-center bond of the 2-methyl group to the manganese. They exhibit temperature dependent 1H NMR spectra due to a hindered rotation of the 2-methyl group with a barrier of activation of AG* = 40-43 kJ ·mol -1. There is evidence for an equilibrium of the complexes 4 and 6 with the isomers tricarbonyl-η3:CH-1-methylene-2-methyl-5-cyclononen-2-yl-manganese (4′), and tricarbonyl-η3:CH-1-methylene-2,5,7-trimethyl-5-cyclononen-2-yl-manganese (6′). At higher temperatures the isomers 4, 4′ and 6, 6′ are interconverted by a 1,4-H shift with a barrier of activation of AG* = 75 kJ · mol-1. The crystal and molecular structure of 4 was determined by X-ray structure analysis. The constitutions of the complexes 4-7 were deduced from IR and 1H NM R spectra.
Cycloadditionen, XIX. Umsetzungen von Butadiinyl- und Hexatriinyl-amin-Derivaten mit Nitriloxiden /Cycloadditions, XIX. Reactions of Butadiynyl- and Hexatriynyl-amine Derivatives with Nitrile Oxides
Authors: Himbert Gerhard , Faul Dieter , Barz Michael
Published: March 2015

Butadiyn- and hexatriynamines 1 a - g, bearing silyl-, trichlorvinyl- and amino groups, resp. in the ω-position of their acetylenic system add nitrile oxides 3 at their first C/C-triple bond to give the 5-aminoisoxazoles 4, whereas the analogous oligoynamines 1 i-l, bearing a hydrogen in the ω-position, add the nitrile oxides 3 at their terminal C/C-triple bond to give the (5-isoxazolyl)ethynyl- or -1,3-butadiynyl-amines 7. The latter ones react with a second molecule of nitrile oxide 3 to give the bis(isoxazoles) 8. In two cases, keton oximes 6e,j are formed as the products of a 1,3-addition.
Thiocarbonylkomplexe des Eisens, VII [1] / Thiocarbonyl Complexes of Iron, VII [1]
Authors: Petz Wolfgang , Weller Frank
Published: March 2015

Slow addition of Fe(CO)4CS (1) to an excess of P(NMe2)3 (2) in pentane produces S=P(NMe2)3 (3) and a tar-like material from which small amounts of violet crystals of

(4) could be isolated. 4 crystallizes in the space group P 21/c, Z = 4, a = 13.124(1), b = 14.131(2), c = 14.070(1) Å; β = 91.71(1)°. The iron atom is trigonal-bipyramidally coordinated and bears a chelating ligand formed by C–C coupling between the former CS group and one CO group of 1 and an additional S atom, incorporated probably via the sulfide 3. One P(NMe2)3 unit coordinates at the iron atom and the other one at the former thiocarbonyl carbon atom.
Reaktive E=C(p-p)π-Systeme, XXVIII / Reactive E=C(p-p)π-Systems, XXVIII
Authors: Grobe Joseph , Le Van Duc , Großpietsch Thomas
Published: March 2015

The reaction of perfluoro-2-phosphapropene F3CP=CF2 (1) with tert-butylamine or isopropylamine in a 1:3 molar ratio leads to the novel iminomethylene phosphanes F3CP=C=N(tBu) [(2), 30% yield] and F3CP=C=N(iPr) [(3), 5%], respectively. 2 slowly decomposes at room temperature giving tert-butylisonitrile and the cyclophosphanes (F3CP)n (n = 3, 4, 5). 3 is found to be less stable than 2 and for example is attacked by primary amines. The reaction of 2 with 2,3-dimethyl-1,3-butadiene or trimethylphosphane yields, on the one hand, the cycloaddition product of bis(trifluormethyl)diphosphene (4), and on the other hand, the phosphorus ylid Me3P=PCF3 (5) together with (tBu)NC.

2 and 3, respectively, are not obtained from (F3C)2PH and the corresponding primary amines in a series of HF elimination and H2NR addition reactions. The main products formed from a 1:4 molar mixture of (F3C)2PH and H2N(iPr) in a one-pot procedure were shown to be the chiral phosphanes F3CP[NH(iPr)]C[=N(iPr)]H (6), F3CP[NH(iPr)]CHF2 (7) and F3CP[NH(iPr)]CH2F (8) (60:35:5). The corresponding reaction of (F3C)2PH with H2N(tBu) mainly yields the compound F3CP[NH(tBu)]CH2F (10).
Synthese und Kristallstrukturen der Polyselenido-Mercurate (PPh4)2[Hg(Se4)2] und [Cs(18-Krone-6)]2[Hg2(Se4)3] / Syntheses and Crystal Structures of the Polyselenido Mercurates (PPh4)2[Hg(Se4)2] and [Cs(18-Crown-6)]2[Hg2(Se4)3]
Authors: Magull Sylvia , Neumüller Bernhard , Dehnicke Kurt
Published: March 2015

(PPh4)2[Hg(Se4)2] has been prepared by the reaction of (PPh4)2[Sn(Se4)3] with Hg(CH3COO)2 in dimethylformamide (DMF) solution. [Cs(18-crown-6)]2[Hg2(Se4)3] has been prepared by the reaction of a lithium polyselenide solution in DMF with Hg(CH3COO)2 in the presence of CsBr and 18-crown-6. Both compounds are obtained as dark red crystals and characterized by X-ray structure determinations.

(PPh4)2[Hg(Se4)2]: Space group P21/c, Z = 4, 3021 observed unique reflexions, R = 0.082. Lattice dimensions at 20 °C: a = 1046.0(3), b = 2129.4(2), c = 2213.1(3) pm,β = 97.62(2)°. The compound consists of PPh4
+ ions and anions [Hg(Se4)2]2-, in which the mercury atom is a spirocenter of puckered HgSe4 rings.

[Cs(18-crown-6)]2[Hg2(Se4)3]: Space group Ia, Ζ = 4, 2859 observed unique reflexions, R = 0.074. Lattice dimensions at 20 °C: a = 2018(1), b = 1097.0(2), c = 2317.1(5) pm, β = 99.40(3)°. The compound forms an ion triple which originates from Cs ··· Se contacts of 382 to 390 pm with the [Hg2(Se4)3]2- ion. The latter can be described as a [Hg(Se4)2]2- ion, which has contacts with a HgSe4 fragment.
Das Isosterenpaar SiO/PN, II [ 1, 2] / The SiO/PN Isoelectronic Pair, II [1, 2]
Authors: Wannagat Ulrich , Burgdorf Doris , Bürger Hans , Pawelke Gottfried
Published: March 2015

The title compounds have been prepared by the reaction of N-chloro-trimethylsilylamino substituted SiCl4 and (Cl3Si)2O with PCl3. Their boiling points, mass spectra and vibrational spectra are compared with those of the isoelectronic perchloro-di-, -tri- and -tetrasiloxanes. In spite of their analogous structures and similar masses, the phosphaniminosilane derivatives are much less volatile than the analogous siloxanes. The mass spectra of both groups of compounds reveal very similar fragmentation patterns. A pronounced feature of the PNSi derivatives is the high wavenumber (∼1375 cm-1) of the PN stretching vibration. This is consistent with an enhanced PN bond order and a bond polarity +P—N- as suggested by other observations.
Synthese und Reaktionen von 2-N,N-Bis(trimethylsilyl)aminobenzonitril – Kristallstrukturen von N≡C(C6H4)N = MoCl3 · 3 MeCN und [(Me3Si)2N(C6H4)CN]2TiCl4 / Synthesis and Reactions of 2-N,N-Bis(trimethylsilyl)aminobenzonitrile – Crystal Structure of N=C(C6H4)N=MoCl3 · 3 MeCN and [(Me3Si)2N(C6H4)CN]2TiCl4
Authors: Roesky Herbert W. , Meller-Rehbein Birgit , Noltemeyer Mathias
Published: March 2015

The 2-(Me3Si)2N(C6H4)CN (1), reacts with NbCl5, MoCl5 and WCl6 to give the nitrogen complexes NC(C6H4)N = NbCl3 (2), NC(C6H4)N = MoCl3·3 MeCN (3) and NC(C6H4)N = WCl4 (4), and with TiCl4 to form the coordination product [(Me3Si)2N(C6H4)CN]2TiCl4 (5). The crystal structures of 3 and 5 are reported.
Modellsysteme für die Gallium-Extraktion, II / Model Systems for Gallium Extraction, II
Authors: Schmidbaur Hubert , Lettenbauer Josef , Kumberger Otto , Lachmann J. , Müller Gerhard
Published: March 2015

The introduction of a methyl substituent in the 2-position of 8-oxy-quinoline strongly alters its ligand properties in the complex formation with gallium(III). From aqueous solutions (ammonium acetate buffer, acetic acid, gallium nitrate) a pale-green complex (2-MeOx)2GaOAc is precipitated instead of the tris(oxinate) chelate. According to a single crystal X-ray diffraction study, the gallium atom is pentacoordinate in this complex, with two chelating 2-MeOx and one monocoordinate acetate ligands. Similar acetato complexes were generated with equally hindered 2,4-dimethyl- and 2,5,7-trimethylquinoline, as well as with 2-ethyl- and 2-n-propylquinoline ligands. Retaining the 2-MeOx ligand, acetate OAc could be exchanged for trifluoroacetate, propionate, cyanoacetate, and (in binuclear complexes) equivalents of succinic, maleic, fumaric, and acetylenedicarboxylic acid. From this series, crystal and molecular structures have also been determined for (2-MeOx)2GaOC(O)CH2CN and [(2-MeOx)2GaOC(O)CHJ2]2 (with crystal nitrobenzene). In the cyanoacetate, the nitrile function is not involved in intra/intermolecular metal coordination. In the binuclear succinate the molecule has a crystallographical center of inversion. As in the cyanoacetate, the environment of the two equivalent gallium centers of the succinate is very similar to that of the acetate complex.
Notizen: 3-Diethylamino-5-phenyl-1,2,4-dithiazolium-hexachlorodicuprat(II) und -tetrachlorocuprat(II), (dpd)2Cu2Cl6 und (dpd)2CuCl4 / 3-Diethylamino-5-phenyl-1,2,4-dithiazolium Hexachlorodicuprates(II) and Tetrachlorocuprates(II), (dpd)2Cu2Cl6 and (dpd)2CuCl4
Authors: Hartung Jürgen , Beyer Lothar , Fernández Vicente , Tudela David , Gutiérrez-Puebla Enrique
Published: March 2015

(dpd)2Cu2Cl6 has been prepared by the reaction of bis(1,1-diethyl-3-benzoyl-thioureato)-copper(II) with SOCl2 in nitromethane. The brown air stable crystals were characterized by X-ray structure determination. Space group P21/n, Z = 4, 4222 observed unique reflexions, R = 0.053, Lattice dimensions (22 °C): a = 1336.4(2), b = 1677.2(9), c = 749.3(2) pm; β = 92.46(2)°. Similar reaction in acetonitrile yields stable orange crystals of (dpd)2CuCl4.
Notizen: Reaktionen von Me2NC(S)SN(SiMe3)2 mit Metallhalogeniden — Kristallstruktur von Me2NCS2ZrCl3 · 3 Pyridin / Reactions of Me2NC(S)SN(SiMe3)2 with Metal Halides – Crystal Structure of Me2NCS2ZrCl3 · 3 Pyridine
Authors: Roesky Herbert W. , Meller-Rehbein Birgit , Noltemeyer Mathias
Published: March 2015

Me2NC(S)SN(SiMe3)2 (1) reacts with TeCl4 and NbCl5 to yield Me2NC(S)SNTeCl2 (4) and Me2NC(S)SNNbCl3 (5), while the dithiocarbamate complexes 6 and 7 are formed with ZrCl4 and HfCl4. The crystal structure of 6 is reported. The reaction of Me2NC(S)SN=TiCl2·3 py 2 with LiN(SiMe3)2 gives the tricyclic compound 8.
Notizen: Synthesis and Structure of a 2,4,5-Tris(methylene)-1-bora-3-silacyclopentane Derivative
Authors: Man Wong Wee Choy Wong Chi , Pritzkow Hans , Siebert Walter
Published: March 2015

3,3-Dimethyl-(e)-1-chlorodimethylsilyl-1-chloro-dimethylaminoboryl-butene-1 (5) reacts with 3,4-dilithio-2,5-dimethyl-2,4-hexadiene in diethylether to give colorless 2-(tert-butylmethy-lene)-4,5-bis(dimethylmethylene)-1-dimethylamino-3-dimethyl-1-bora-3-sila-cyclopentane (4) in 41% yield. The X-ray structure analysis shows a non-planar ring with a small angle C2-Si3-C4 = 94.9(1)°.
Heterometallische Cluster durch ligandunterstützte Metallfragmentkondensation / Heterometallic Clusters by Ligand Assisted Metal Fragment Condensation
Authors: Rohde Wolfgang , Fendesak Gert
Published: March 2015

Dicobalt complexes of 3-vinylpropargylic alcohol derivatives react with biscyclooctenetricarbonyliron to give new chelate complexes of the iron tricarbonyl fragment with the olefinic double bond and the alcohol oxygen atom bound to the iron fragment. These compounds react upon heating in an inert solvent to give FeCo-alkynyl cluster complexes in high yields. One of these compounds has been structurally characterized by X-ray crystallography.