Published by De Gruyter

Volume 58 Issue 1

Issue of Zeitschrift für Naturforschung B

Contents
Journal Overview

June 2, 2014

Dinuclear Derivatives of Mn₂(CO)₁₀ with the Ligand Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane, P(C₇H₇)₃, and their Oxidative Cleavage

Max Herberhold, Wolfgang Milius, Andreas Pfeifer

Page range: 1-10

Abstract

The photo-induced reaction of Mn 2 (CO) 10 with the olefinic phosphane P(C 7 H 7 )3 (1; [P] if coordinated to a metal) leads stepwise to the axially substituted derivatives ax-{Mn 2 (CO) 9 [P]} (2) and ax,ax-{Mn 2 (CO) 8 [P] 2 } (3). Oxidative cleavage of 3 by halogens gives cis-{Mn(X)(CO) 4 [P]} (X = Cl (4a), Br (4b), I (4c)), whereas oxidation of 3 with NOBF 4 provides a route to the salt {Mn(CO) 4 [P]}BF 4 (5) which is also accessible by halide abstraction from 4b by AgBF 4 . The reactivity of the bromo complex 4b has been studied, and analogues such as cis-{Mn(R)(CO) 4 [P]} (R = Me (4d), Fc (4e) and N( i Pr) 2 (4f)) have been prepared. The displacement of a carbonyl ligand from 4b by iodide leads to mer-{Mn(I)(CO) 3 [P]} (6c) and by 1 to mer,trans-{Mn(Br)(CO) 3 [P] 2 } (7b). The complexes mer-{Mn(X)(CO) 3 [P]} (6a-c) are obtained by splitting the dimers, Mn 2 (CO) 6 (CH 3 CN) 2 - (μ −X) 2 (X = Cl, Br, I), with P(C 7 H 7 ) 3 (1). The cation in 5 and the halogeno compounds 6a-c contain [P] (1) as a chelating four-electron ligand which uses one cyclohepta-2,4,6-trienyl substituent for π-complexation. The coordinated double bond in 6c can be displaced by phosphites P(OR)3 (R = Me, Et) to give fac-{Mn(I)(CO) 3 [P(C 7 H 7 ) 3 ][P(OR) 3 ]} (8c). The structures of the new complexes 2-8 have been assigned on the basis of their carbonyl stretching absorption patterns in the IR spectra and by their NMR spectra ( 1 H, 13 C, 31 P). Single-crystal X-ray structure analyses have been carried out for 3 and 6c.

June 2, 2014

Synthesis and Reactivity of Bromo-Mer-Tricarbonyl-Trans-Bis[Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane]-Manganese, Mnbr(CO)₃[P(C₇H₇)₃]₂

Max Herberhold, Wolfgang Milius, Andreas Pfeifer

Page range: 11-15

Abstract

The reaction of Mn(X)(CO) 5 (X = Cl, Br, I) with 2 equivalents of tri(1-cyclohepta-2,4,6- trienyl)phosphane, P(C 7 H 7 ) 3 ((1); [P] if coordinated to a metal) led stepwise first to cis- {Mn(X)(CO) 4 [P]} (X = Cl (4a), Br (4b), I (4c)) and then to mer,trans-{Mn(X)(CO) 3 [P] 2 } (X = Cl (5a), Br (5b), I (5c)). Nucleophilic displacement of the bromo ligand from (5b) by one-, threeor five-electron ligands gave the pseudohalide complexes mer,trans-{Mn(X)(CO) 3 [P] 2 } (X = NCO (5d) and NCS (5e)), the acetylacetonate derivative Mn(acac)(CO) 2 [P] 2 (6) and the halfsandwich complexes CpMn(CO)2[P] (7) or TpMn(CO) 3 (8). According to the X-ray structure determination of 5e the thiocyanate ligand is N-coordinated.

June 2, 2014

Transition Metal-Gallium Ordering In HfCoGa2 And HfNiGa₂

Martin Schlüter, Birgit Heying, Rainer Pöttgen

Page range: 16-21

Abstract

The gallides HfCoGa 2 and HfNiGa 2 were synthesized by arc-melting of the elements and subsequent annealing in glassy carbon crucibles. Their structures have been reinvestigated by X-ray diffraction on powders and single crystals: I4mm, a = 1222.4(1), c = 812.0(1) pm, wR2 = 0.0766, 1464 F 2 values, 64 variables, BASF = 0.41(2) for HfCoGa 2 and a = 1224.0(2), c = 809.3(2) pm, wR2 = 0.0609, 1499 F 2 values, 63 variables for HfNiGa 2 . In contrast to a previous investigation (Dopov. Akad. Nauk Ukr. RSR, Ser. A, 51 (1988)) we observe a fully ordered arrangement of the transition metal and gallium atoms. The crystal chemistry of these gallides is briefly discussed.

June 2, 2014

Metal Directed One-Pot Syntheses: Mono-, Di- and Tetra-Nuclear Clusters [1]

Rolf W. Saalfrank, Uwe Reimann, Frank Hampel, Cornelia Goebel, Regine Herbst-Irmer

Page range: 22-26

Abstract

Upon reaction of HL 1 1 (picoline-tetrazolylamide) with cobalt(II) acetate under aerobic conditions or with copper(II) acetate, the mono-nuclear complex [Co III (L 1 ) 3 ] 3 and the di-nuclear complex [Cu 2 (L 1 ) 4 ] 4 were generated. In 3 and 4, (L 1 ) − exclusively coordinates across its nitrogen donors. However, when HL 2 5 (picoline-tetrazolylthioamide) was reacted with copper- or nickel acetate, the di-nuclear cluster [Cu 2 (L 2 ) 4 ] 6 and the tetra-nuclear cluster [Ni 4 (L 2 ) 8 ] 7, respectively, were isolated. Contrary to 3 and 4, in 6 and 7, (L 2 ) − also coordinates across sulfur.

June 2, 2014

Quadratate Und Hydrogenquadratate Cyclischer Stickstoffbasen Mit Schicht-, Ketten- und Leiterstrukturen / Squarates and Hydrogensquarates of Cyclic Nitrogen Bases with Layer-, Chainand Ladder-Structures

Rainer Mattes, Jörg Ebbing, Annette Grüss, Jens Köppe, Krystyna Majcher

Page range: 27-35

Abstract

The synthesis and single crystal X-ray structures of four adducts of squaric acid with cyclic nitrogen bases are reported. Extensive hydrogen bonding, ionic interactions and (in one case) π-π-interactions lead to layered, and to two- and three-dimensional assemblies. [Pyrimidinium][ hydrogenquadratate] (1) has a layer structure, consisting of head-to-tail infinite chains of pyrimidinium and [HC 4 O 4 ]− ions, which are cross-linked by short N-H···O and C-H···O hydrogen bonds. [C 9 H 11 N 2 ][HC 4 O 4 ] ・0.5H 2 C 4 O 4 (2), the adduct of a benzodiazepin and squaric acid, has a ladder-structure. Chains of [HC 4 O 4 ] − ions and H 2 C 4 O 4 molecules in alternating order form the ladder-beam. Layers of cations and anions in the ratio 2:1 build the crosspieces at an angle of 49° to the beam. The layers contain dimers of [HC 4 O 4 ] − ions. [H 2 L 2 ][HC 4 O 4 ] 2 (3) with L 2 = 5,6,7,8,9,14,15,16,17,18-decahydrodibenzo[e,l]-1,4,8,11-tetraaza-cyclotetradecine shows zigzag chains made of [HC 4 O 4 ] − ions. Between the [H 2 L 2 ] 2+ and the [HC 4 O 4 ] − ions π-π interactions exist besides up to four N-H···O hydrogen bonds. The [H 2 L 2 ] 2+ ions possess two different conformations. [H 2 cyclam][C 2 O 4 ] ·4H 2 O (4) contains strongly undulated layers of the composition [C 4 O 4 ·4H 2 O] 2− . The cations, which show two intramolecular N-H···N hydrogen bonds with N···N distances of 2.870 (3) Å , are interlinked at an angle of 41.5°.

June 2, 2014

Tungstenmethyl-Dimethylsilanols Cp(Oc)₂(R₃P)W—CH₂—SiMe₂OH (R = Me, Ph) – Synthesis Via Oxygenation or Hydrolysis

Marco Hofmann, Wolfgang Malisch, Heike Hupfer, Martin Nieger

Page range: 36-43

Abstract

The tungstenmethyl-dimethylsilanols Cp(OC) 2 (R 3 P)W-CH 2 -SiMe 2 OH [R = Me (6a), Ph (6b)] have been synthesized by oxofunctionalization of the tungstenmethyl-silanes Cp(OC) 2 (R 3 P)W- CH 2 -SiMe 2 H [R = Me (3a), Ph (3b)] with dimethyldioxirane. 6a has been additionally obtained by Et 3 N-assisted hydrolysis of the tungstenmethyl-chlorosilane Cp(OC) 2 (Me 3 P)W-CH 2 - SiMe 2 Cl (5). Compounds 6a,b are stable with respect to self-condensation, but controlled condensation of 6a with Me 2 Si(H)Cl in the presence of triethylamine has been realized to give the tungstenmethyl-substituted disiloxane Cp(OC) 2 (Me 3 P)W-CH 2 -SiMe 2 O-SiMe 2 H (7). The new compounds have been identified IR- and NMR-spectroscopically and, in the case of 3a, by X-ray analysis.

June 2, 2014

Reaktionen von Vanadium(V)- und Tantal(V)-Komplexen Mit Kinetisch Stabilisierten Phosphaalkinen. Einfache Synthese von 1,3,4-Thia- und 1,3,4-Selenadiphospholen / Reactions of Vanadium(V) and Tantalum(V)-Complexes with Kinetically Stabilized Phosphaalkynes. A Simple Synthesis of 1,3,4-Thia and 1,3,4-Selenadiphospholes

Christoph Peters, Uwe Fischbeck, Frank Tabellion, Manfred Regitz, Fritz Preuss

Page range: 44-51

Abstract

A simple synthetic pathway to the unknown 1,3,4-thiadiphospholes 3 and 1,3,4- selenadiphospholes 4 has been developed involving reactions of the azaphosphavanada(V)- cyclobutenes 2, generated in situ from the imidovanadium(V) complex tBuN = VCl 3 and the phosphaalkynes 1a - d, with an excess of elemental sulfur or grey selenium, respectively. The reactions of the phosphaalkynes 1a,b with TaOCl 3 or VOCl 3 · DME furnish the 1,2-dichloro-phosphaalkenes 5a,b and 1,2,3,4-tetrachloro-3,4-di-tert-butyl-1,1-diphosphethane 7a. The metallacyclic species 2e - h with secondary or primary alkyl groups on the ring nitrogen atom are unstable and undergo quantitative conversion to the 1H-1,2,4-azadiphospholes 8, whereas in the presence of an excess of phenylacetylene the 1H-1,2-azaphospholes 9e - h, are formed selectively. A catalytic reaction course has been demonstrated for the cyclotrimerization of phenylacetylene and 2-butyne initiated by small amounts of TaSCl 3 . The syntheses of the vanadium(IV) complexes [tBuN = VCl 2 · 2Py] and [ t BuN = VCl 2 · TMEDA] are also described starting from t BuN = VCl 3 and phosphaalkene 12.

June 2, 2014

New Coordination Polymers Based On Transition Metal Squarates And Pyrazine Ligands

Christian Näther, Jan Greve, Inke Jeß

Page range: 52-58

Abstract

Three new coordination polymers have been prepared by hydrothermal reaction of squaric acid, pyrazine and the metal halides FeCl 2 · 4H 2 O, CoBr 2 and NiBr 2 . In their crystal structures the metal atoms are coordinated by four water molecules and two pyrazine ligands within slightly distorted octahedra. The pyrazine ligands connect the metal atoms via μ-N,N’-coordination to linear chains which are connected via hydrogen bonding. The squarate dianions are not coordinated to the metal atoms and are located between the chains. The thermal behaviour of all compounds was investigated using TG-DTA-MS measurements. A complex behaviour for all compounds is found and the decomposition temperatures increase from Fe to Ni. From these investigations there are no hints for the occurrence of stoichiometric intermediate compounds.

June 2, 2014

Peri-Interactions in Naphthalenes, 9 [1]. On Hypercoordination in Non-Quaternary Phosphonium Salts and a Secondary Phosphine with the (8-Dimethylamino-Naphth-1-Yl) Substituent

Günter Paulus Schiemenz, Christian Näther, Simon Pörksen

Page range: 59-73

Abstract

The 31 P NMR data of non-quaternary (8-dimethylamino-naphth-1-yl)phosphonium salts, with emphasis on the 1 J( 31 P, 1 H) coupling constants, where scrutinized for their potential to yield information about N→P dative interactions. As for δ ( 29 Si) and 1 J( 29 Si, 1 H) in the isosteric silanes, the data do not permit conclusions in favour of such interactions. 1 J( 31 P, 1 H) of bis(8-dimethylaminonaphth- 1-yl)phosphine in conjunction with the distances d(N···P) invalidates the basic assumption on which the claim of dative N→P/Si bonding in such phosphorus and silicon compounds rests, viz. that N···P/Si distances of ca. 270 pm are evidence for P/Si-hypercoordination. No evidence for hydrogen bonds N···H-P was found.

June 2, 2014

The Hexakis(N,N'-Dimethylurea)Cobalt(Ii) Cation: A Flexible Building Block for the Construction of Hydrogen Bonded Networks

Giannis S. Papaefstathiou, Robby Keuleers, Constantinos J. Milios, Catherine P. Raptopoulou, Aris Terzis, Herman O. Desseyn, Spyros P. Perlepes

Page range: 74-84

Abstract

The ligand N.N'-dimethylurea (DMU) is used to propagate the octahedral coordination geom- etry of [Co(DMU) 6 ] 2+ into 1D and 2D assemblies via a combination of coordinative bonds and interionic hydrogen-bonding. Compounds [Co(DMU) 6 ](ClO 4 ) 2 (1), [Co(DMU) 6 ](BF 4 ) 2 (2) and [Co(DMU) 6 ](NO 3 ) 2 (3) have been prepared from the reactions of DMU and the appropriate hydrated cobalt(II) salts in EtOH. MeCN or Me 2 CO (only for 1) in the presence of 2,2-di- methoxypropane. Crystal structure determinations demonstrate the existence of [Co(DMU) 6 ] 2+ cations and CIO 4 - , BF 4 - or NO 3 - counterions. The great stability of the [Co(DMU) 6 ] 2+ cation in the solid state is attributed to a pseudochelate effect which arises from the existence of strong intracationic N-H···O(DMU) hydrogen bonds. The [Co(DMU) 6 ] 2+ cations and counterions self- assemble to form a hydrogen-bonded ID architecture in 1, and different 2D hydrogen-bonded networks in 2 and 3. The precise nature of the resulting supramolecular structure is influenced by the nature of the counterion. Two main motifs of intermolecular (interionic) hydrogen bonds have been observed: N-H ···O(ClO 4 - , NO 3 - ) or N-H ··· F(BF 4 - ) and weak C-H F(BF 4 - ) or C-H-O(NO 3 - ) hydrogen bonds. The complexes were also characterized by vibrational spec- troscopy (IR, far-IR. low-frequency Raman). The spectroscopic data are discussed in terms of the nature of bonding and the know;n structures.

June 2, 2014

Metallkomplexe von Biologisch Wichtigen Liganden, CXLVIII [1]. Katalytische Peptidsynthese aus Glycinester miit Hilfe von Triflaten Und Cloriden der Seltenen Erden, sowie von Metall(III), (IV), (V) und (VI)-Chloriden / Metal Complexes of Biologically Important Ligands, CXLVIII [1]. Synthesis of Peptides from Glycine Ester Catalysed by Triflates and Chlorides of Metal(III, IV, V And VI) Ions

Jan Schapp, Wolfgang Beck

Page range: 85-91

Abstract

Formation of di- and triglycine ethylester which were determined by HPLC after derivatisation with dansyl chloride was observed in medium to high yields from CH 2 Cl 2 solutions of glycine ethylester in the presence of metal triflates and metal chlorides: FeCl 3 (yield 82%), AlCl 3 (73%), GdCl 3 (56%), La(OTf) 3 (59%), Sc(OTf) 3 (55%), ZrCl 4 (62%), HfCl 4 (60%), VOCl 3 (43%), TaCl 5 (29%). Esters of higher α-amino acid esters (AlaOMe, PheOMe) gave lower yields in peptide formation.

June 2, 2014

Metallkomplexe mit Biologisch Wichtigen Liganden, CIL [1]. Metallorganische η²-N,O-Lysinato-Komplexe / Metal Complexes Of Biologically Important Ligands, Cil [1]. Organometallic η²-N,O-Lysinato-Complexes

Walter Ponikwar, Wolfgang Beck

Page range: 92-96

Abstract

η 2 -N,O-Chelate complexes LnM[NH 2 CH(CO 2 )CH 2 CH 2 CH 2 CH 2 NH + 3 Cl - ] with L-lysinate in the protected ω-ammonium form (L n M = (allyl) 2 Rh, (2-pyridylphenyl) 2 Ir, (p-cymene)(Cl)Ru, (C 6 Me 6 )(Cl)Ru, (C 5 Me 5 )(Cl)Rh, (C 5 Me 5 )(Cl)Ir) were obtained from chloro bridged complexes. A heterometallic lysinate bridged complex Cp*(Cl)IrNH 2 CH(CO 2 )(CH 2 ) 4 NH 2 Ir(Cl)Cp* is formed with Cp*(Cl)Ir(N,O-lysinate·HCl) and [Cp*RhCl 2 ] 2 .

June 2, 2014

Synthese monofluorierter cyclopropanoider Nucleosidanaloga / Synthesis of Monofluorinated Cyclopropanoic Nucleoside Analogues

René Csuk, Gisela Thiede

Page range: 97-105

Abstract

A novel class of cyclopropanoid monofluorinated nucleoside analogues was easily prepared starting from a suitable protected (fluorocyclopropyl)methanol derivative.

June 2, 2014

Hydroxyurea Analogues of Fosmidomycin

Thomas Kurz, Detlef Geffken, Claudia Wackendorff

Page range: 106-110

Abstract

Benzyloxyureas (4) have been prepared by reactions of diethyl 3-benzyloxyamino-propyl-phosphonate (3) with isocyanates, potassium cyanate or 1,1’-carbonyldiimidazole / methylamine. Conversion of phosphonic esters 4 into phosphonic acids 6 by means of bromotrimethylsilane and catalytic hydrogenation of 4, 6 afforded the target compounds 5, 7.

June 2, 2014

Synthesis of 2-Phenylisothiazol-3(2H)-One 1,1-Dioxides: Inhibitors of Human Leukocyte Elastase

Michael Gütschow, Markus Pietsch, Kathleen Taubert, Tonia H. E. Freysoldt, Bärbel Schulze

Page range: 111-120

Abstract

A series of 2-phenylisothiazol-3(2H)-one 1,1-dioxides 14a - q were synthesized by oxidation of isothiazolium perchlorates 12. The inhibition of the serine proteases cathepsin G, chymotrypsin and human leukocyte elastase (HLE) by 14 was investigated. Some 4,5-diphenyl substituted derivatives ( 14i - k) were found to inhibit HLE in a time-dependent manner and exhibited k obs /[I] values > 500 M −1 s −1 . 14k (k obs /[I] = 2400 M −1 s −1 ), was the most potent HLE inhibitor of this series. Kinetic investigations led to the conclusion that 2-phenylisothiazol-3(2H)-one 1,1-dioxides interact with HLE at the active site as well as at another binding site, resulting in a complex type of inhibition.

June 2, 2014

Erratum

Page range: 121-121

June 2, 2014

The Reduction of Pyridine to 1,4-Dihydropyridine by Lithiumtetrahydroborate in the Presence of Water

Heinrich Nöth, Marcus Warchhold

Page range: 123-126

Abstract

In the presence of water lithium tetrahydroborate is capable of reducing pyridine to 1,4- dihydropyridine. The product, lithiumtetrakis(pyridine) tetrakis(1,4-hydropyridyl)borate, was isolated and characterized by NMR and IR spectroscopy and single crystal X-ray diffraction. [Li(py) 4 ][B(pyH) 4 ].2(1,4-dioxane) crystallized in space group P4 2 /n, Z = 2. Similarly, NaBH4 can also reduce pyridine in the presence of water and equivalent amounts of LiCl or ZnCl 2 .

June 2, 2014

Preparation, Crystal and Magnetic Structure of the Double Perovskites Ca₂TWO₆ (T = Co, Ni)

M.J. Martínez-Lope, J.A. Alonso, M.T. Casais, M.T. Fernández-Díazb

Page range: 127-132

Abstract

Ca 2 TWO 6 (T = Co, Ni) perovskites have been prepared in polycrystalline form by thermal treatment, in air, of previously decomposed citrate precursors. These materials have been studied by X-ray (XRD) and neutron powder diffraction (NPD) data. Our results show that these compounds crystallize, at room temperature, in the monoclinic space group P2 1 /n. The two perovskites contain divalent T (T = Co, Ni) cations. The low temperature antiferromagnetic ordering has been followed from sequential NPD data. Peaks of magnetic origin appear at the NPD patterns below temperatures of T N = 36 K and T N = 56 K for the Co and Ni compounds, respectively. The magnetic structures are both defined by a propagation vector k = (1/2, 0, 1/2), and can be described as an array of ferromagnetic layers of Co(Ni) moments, perpendicular to the [101] directions, coupled antiferromagnetically.

June 2, 2014

Hydroboration of Bis(Trimethylsilyl)Ethyne. New Aspects of Hydroboration

Bernd Wrackmeyer, Oleg. L. Tok, Wolfgang Milius, Moazzam H. Bhatti, Saqib Ali

Page range: 133-138

Abstract

The hydroboration of bis(trimethylsilyl)ethyne, Me 3 Si-C≡C-SiMe 3 1, with 9-borabicyclo [3.3.1] nonane (9-BBN) gives first the expected (Z)-alkene 5 which rearranges, without UV irradiation, after several days quantitatively into the (E)-alkene 6. Heating of 6 in the presence of a further equivalent of 1 leads, again almost quantitatively, to an allene, the 1,1,4,4-tetrakis(trimethylsilyl)-4-[9-(9- borabicyclo[3.3.1]nonyl)]buta-1,2-diene 8. Reactive structures arising from π-σ delocalisation involving the boryl group are proposed to be responsible both for the cis/trans-isomerisation and the allene formation. It is suggested that analogous structures may explain the previously observed formation of allenes 9 and 10, tin-analogues of 8. The structures of 5, 6 and 8 in solution follow from a consistent set of NMR data ( 1 H, 11 B, 13 C, 29 Si NMR), and the solid-state structure of 8 was confirmed by X-ray analysis.

June 2, 2014

Conductivity, Electrodeposition and Magnetic Property of Cobalt(II) and Dysprosium Chloride in Zinc Chloride-1-Ethyl-3-Methylimidazolium Chloride Room Temperature Molten Salt

Hsin-Yi Hsu, Chao-Chen Yang

Page range: 139-146

Abstract

Electric conductivity of the molten zinc chloride-1-ethyl-3-methylimidazolium chloride phases has been measured by a computerized system using the d.c. four-probes method. The sequence of the conductivities for the different component melts is ZnCl 2 -EMIC > ZnCl 2 -EMIC-CoCl 2 > ZnCl 2 - EMIC-DyCl 3 > ZnCl 2 -EMIC-CoCl 2 -DyCl 3 . The results may be explained in terms of the viscosity increase due to the complex formation. The electrochemistry and the nucleation mechanism of cobalt(II) or/and dysprosium chloride in acidic ZnCl 2 -EMIC melts have been investigated by cyclic voltammetry and chronoamperometry at different temperatures, respectively. The results of the SEM and VSM analyses reveal that reduction of Dy 3+ to Dy 2+ may have occurred, while reduction of Dy 3+ to Dy(0) is conjectured to play no role. Moreover, the results of chronoamperometry experiments show that nucleation in the alloy electrodeposition is instantaneous, and that, as the applied deposition potential becomes more negative, the nucleation density increases, which rapidly shortens the time required for the diffusion zones to overlap. Electrodeposition of a Dy-Co-Zn alloy on a Ni or Cu sheet from the 50-50 mol% ZnCl 2 -EMIC melt containing 1.687 mol% CoCl 2 and 1.114 mol% DyCl 3 has been accomplished, and the morphology and the composition have been analyzed by SEM and EDS, respectively. The magnetism of the deposited layer is discussed based on the results of the VSM analysis.

June 2, 2014

A Zwitterionic Platinum Complex with a Carbene Ligand

Thiemo Marx, Lars Wesemann, Siegbert Hagen, Ingo Pantenburg

Page range: 147-150

Abstract

A new stannaborate complex of platinum is prepared from the reaction of [Bu 3 MeN] 2 [trans- (Et 3 Pt) 2 Pt(SnB 11 H 11 )2] and 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (dpdmiy). [trans- (Et 3 P) 2 Pt(SnB 11 H 11 )(dpdmiy)] has been analyzed by X-ray crystallography and NMR spectroscopy.

June 2, 2014

Synthesis and Structural Characterization of the Mixed Ligand Complex [Cu(Hml)₂(Phen)] · 2 H₂O (H₂ml = 2-Methyllactic Acid)

Rosa Carballo, Berta Covelo, Ezequiel M. Vázquez-Lópeza, Alfonso Castiñeiras, Juan Niclós

Page range: 151-154

Abstract

A new mixed-ligand complex of copper(II) with 1,10-phenanthroline and 2-methyllactate was prepared. [Cu(HmL) 2 (phen)] ·2H 2 O (where HmL = monodeprotonated 2-methyllactic acid) was characterized by elemental analysis, IR, electronic and EPR spectroscopy, magnetic measurements at room temperature, thermogravimetric analysis and X-ray diffractometry. The copper atom is in a tetragonally distorted octahedral environment and the 2-methyllactato ligand is bidentately chelating. The presence of lattice water molecules mediates the formation of a three-dimensional network.

June 2, 2014

Synthesis, Thermal and X-Ray Investigations of the High-Temperature Phase of Copper(I) Cyanide

Olaf Reckeweg, Cora Lind, Arndt Simon, J. Salvo

Page range: 155-158

Abstract

CuCN was investigated by chemical analysis, IR spectroscopy and powder X-ray diffraction. A high-temperature phase of CuCN was identified and structurally characterized by Rietveld refinement. HT-CuCN is isotypic to AgCN (R3m (No. 166), Z = 3, a = 597.109(8), c = 484.33(5) pm, Cu (3a), C/N (6c), z = 0.3915(10) at 77 K) with head-tail disorder of the cyanide anions.

June 2, 2014

Rietveld Refinement of the Crystal Structure of α-Be₃N₂ and the Experimental Determination of Optical Band Gaps for Mg₃N₂, Ca₃N₂ and CaMg₂N₂

Olaf Reckeweg, Cora Lind, Arndt Simon, Francis J. DiSalvo

Page range: 159-162

Abstract

α-Be 3 N 2 powder was obtained by reacting Be metal with dry, flowing N 2 at 1600 K. The product contained 5.9(7) wt.% of BeO. The anti-bixbyite structure suggested earlier was verified through Rietveld refinement on the basis of X-ray powder data (Ia3 (#206); a = 814.518(6) pm). The optical band gaps of α-Be 3 N 2 , Mg 3 N 2 and Ca 3 N 2 are compared with newly measured values for Mg 3 N 2 , Ca 3 N 2 and CaMg 2 N 2 .

June 2, 2014

Preparation and Crystal Structure of Hexapotassium-μ-Oxo-Hexathiodititanate(IV), K₆Ti₂OS₆

Kurt O. Klepp, Ferdinand Fabian

Page range: 163-167

Abstract

Pale yellow crystals of the title compound were obtained by reacting an intimate mixture of K 2 S, K 2 S 2 O 4 , Ti and S at 650 °C. K 6 Ti 2 OS 6 is monoclinic, mP60, s. g. P2 1 /c. It is characterized by the formation of bitetrahedral complex anions, [S 3 TiOTiS 3 ] 6− , which adopt a staggered conformation. The mean Ti-S and Ti-O bond lengths are 2.242(1) and 1.836(2) Å , respectively, the Ti-O-Ti bond angle is 153.8(2)°. Two K + ions complete the coordination of the bridging oxygen atom by the cations to a heavily distorted tetrahedral configuration. The anions are arranged in corrugated slabs running parallel to (100). The packing and crystallographic relationship to K 6 Co 2 O 7 are discussed.

June 2, 2014

(Phosphine)Silver(I) Sulfonate Complexes

Patric Römbke, Annette Schier, Hubert Schmidbaur

Page range: 168-172

Abstract

Phosphine)silver(I) organosulfonate complexes of the type (R 3 P)AgOS(O) 2 R’ have been prepared in good yields from the corresponding silver sulfonates and tertiary phosphines in dichloromethane solution [R 3 = Ph 3 , Ph 2 (2-Py), Me 2 Ph, with R’ = 4-Me-C 6 H 4 ; R = Ph, R’ = Et and 2,5-Me 2 -C 6 H 4 ]. If ethanol is present in the reaction mixture, the products contain one equivalent of ethanol. The crystal structures of (Ph 3 P)AgOS(O) 2 (C 6 H 4 -4-Me)(EtOH) (1), and (Me 2 PhP)AgOS(O) 2 (C 6 H 4 -4- Me) (5) have been determined. Complex 1 is present as a dimer in which the monomeric units feature intermolecular Ag-O donor/acceptor bonding in a four-membered ring. The coordination sphere of the silver atoms is further complemented by an ethanol molecule which is also engaged in hydrogen bonding with one of the sulfonate oxygen atoms. The solvent-free complex 5 is associated into helical chains via Ag-O coordinative bonds which provide the silver atoms with a distorted planar T-shaped coordination.

June 2, 2014

Beryllium Dichloride Coordination by Nitrogen Donor Molecules

Martina P. Dressel, Stefan Nogai, Raphael J. F. Berger, Hubert Schmidbaur

Page range: 173-182

Abstract

The reaction of anhydrous beryllium chloride with nitrogen donors L in diethylether as a solvent under mild conditions affords 1:2 complexes of the type L 2 BeCl 2 [L = benzonitrile (1), pyridine (2), 3,5-dimethylpyridine, pyrrolidine, piperidine (8), and diethylamine (10)]. Structural studies of compounds 1, 2, 8 (CHCl 3 ), and 10 have shown that the complexes have the beryllium centers N 2 Cl 2 - tetracoordinated with a distorted tetrahedral geometry of the core unit. In crystals of 8 and 10 these molecules are associated to form helical strings via distinct N-H-Cl hydrogen bonding. The reaction of the weak donor pyrazole (pyz) with (Et 2 O) 2 BeCl 2 at low temperature gives the mixed complex [(Et 2 O)(pyz)BeCl 2 ] (4), in which one diethylether molecule is retained in the inner coordination sphere of the metal. In tetrahydrofuran (thf) solution, no reaction is observed with pyrazole, indicating that tetrahydrofuran is the stronger donor as compared to pyrazole, and the (thf) 2 BeCl 2 solvate remains intact. By contrast, with the strong base pyrrolidine (pyrr) the same reaction leads to substitution of one chloride ligand to give the ionic product [(pyrr) 3 BeCl] + Cl − , (7). Both products (4, 7) have been structurally characterized. At room temperature the reactions with pyrazole or piperidine lead to ether cleavage as a side-reaction which may even become dominant at long reaction times and more forcing conditions. Dinuclear complexes of the type [LBeCl(μ 2 -OR)] 2 are formed, the structures of which have also been determined. The results suggest that hydrogen bonding may assist in the ether cleavage process, since this reaction is not observed for ligands devoid of N-H functions.

June 2, 2014

Zur gezielten Synthese funktionell substituierter Oligosilane aus Silyltriflaten und Aminosilyllithiumverbindungen / Tailor-Made Synthesis of Functional Substituted Oligosilanes from Silyl Triflates and (Aminosilyl)Lithium Compounds

Wolfram Uhlig

Page range: 183-190

Abstract

Diethylamino substituted silyllithium compounds have been prepared in situ from the corresponding phenylchlorosilanes and lithium. These reagents undergo coupling reactions with triflate derivatives of silanes and oligosilanes. Exchange processes analogous to metal halogen exchange and Si-Si bond cleavage, which are side reactions with chlorosilanes, were not observed. Based on the coupling reaction and the amino-to-triflate transformation, functionalized tri-, tetra-, penta- und hexasilanes have been synthesized. α,ω-Triflate substituted oligosilanes containing π-systems have also been obtained. These compounds are useful building blocks for new organosilicon polymers. The formation of the silicon polymers at low temperatures, in short reaction times, and with high yields is reported. The 29 Si NMR spectra indicate a regular, alternating arrangement of the building blocks in the polymer backbone.

June 2, 2014

Secondary Bonding Interactionsi in Some Di- and Trihaloanilinium Halides

Esperanza López-Duplá, Peter G. Jones, Fabiola Vancea

Page range: 191-200

Abstract

Six solvent-free structures of di- and trihaloanilinium halides are presented. All involve clearly defined hydrophilic regions built up from classical hydrogen bonding systems. The 2,4-dibromo-, 2,6- dichloro-, 2,4,6-trichloro- and 2,4,6-tribromoanilinium derivatives form ribbon structures involving annelated R 2 4 (8) rings with NH 2 donors (two hydrogens from the positively charged NH 3 groups) and halide acceptors. The 2,5-dibromo- and 2,4,5-trichloro derivatives form layers with two types of ring, R 2 4 (8) and R 4 8 (16). All structures also involve other secondary interactions (C-H. . . X hydrogen bonds and/or X. . . X contacts, X = halogen), some of which link the ribbons or layers into a second or third dimension. The shortest X. . . X contacts generally involve the anions. In the 2,4-dibromo, 2,4,6-trichloro and tribromo derivatives, somewhat more extensive halogen aggregates (triangles, angled X 3 or X 4 chains) are formed between neutral halogens. In two appendices, the packing patterns of (I) the disordered structure 3,4,5-trichloroanilinium chloride and (II) the known structures of unsubstituted anilinium halides are briefly presented.

June 2, 2014

Ba₉[NbN₄]₂O[Cn₂] – Synthesis, Crystal Structure and Raman Spectrum

Olaf Reckeweg, Francis J. DiSalvo

Page range: 201-204

Abstract

Red transparent single crystals of Ba 9 [NbN 4 ] 2 O[CN 2 ] were synthesised by the reaction of BaO coated Ba metal, C and Nb powder in arc-welded Nb ampoules at 1300 K. The title compound was characterised by X-ray single crystal diffraction (P1̅ , a = 799.05(2), b = 962.61(2) and c = 1264.38(4) pm; α = 75.859(1), β = 85.745(1) and γ = 87.8621(8)°; Z = 2) and Raman spectroscopy (νsym = 1234 and δ = 632/658/668 cm −1 ). It now seems likely that a nitride-azide compound we previously reported, Ba 9 [NbN 4 ] 2 N[N 3 ], does not exist, but is in fact the title compound.

About this journal

Objective
Zeitschrift fuer Naturforschung B (ZNB) publishes novel research in all areas of inorganic chemistry, organic chemistry, and analytical chemistry. In particular, the journal focuses on solid state chemistry, coordination chemistry, main group element chemistry, synthetic organic chemistry, natural product chemistry and, to a lesser extent, on analytical chemistry. For more than 65 years Zeitschrift fuer Naturforschung B has been open to contributions from all fields of experimental and theoretical chemistry. Zeitschrift fuer Naturforschung B publishes 12 issues per volume/year. Sometimes double issues occur.

Topics

Solid state chemistry
Coordination chemistry
Main group element chemistry
Organic chemistry
Natural product chemistry

Article formats
Original (full) papers, research notes and preliminary communications, reports on specific research topics of current interest (reviews)

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Volume 58 Issue 1

Issue of Zeitschrift für Naturforschung B

Dinuclear Derivatives of Mn2(CO)10 with the Ligand Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane, P(C7H7)3, and their Oxidative Cleavage

Abstract

Synthesis and Reactivity of Bromo-Mer-Tricarbonyl-Trans-Bis[Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane]-Manganese, Mnbr(CO)3[P(C7H7)3]2

Abstract

Transition Metal-Gallium Ordering In HfCoGa2 And HfNiGa2

Abstract

Metal Directed One-Pot Syntheses: Mono-, Di- and Tetra-Nuclear Clusters [1]

Abstract

Quadratate Und Hydrogenquadratate Cyclischer Stickstoffbasen Mit Schicht-, Ketten- und Leiterstrukturen / Squarates and Hydrogensquarates of Cyclic Nitrogen Bases with Layer-, Chainand Ladder-Structures

Abstract

Tungstenmethyl-Dimethylsilanols Cp(Oc)2(R3P)W—CH2—SiMe2OH (R = Me, Ph) – Synthesis Via Oxygenation or Hydrolysis

Abstract

Abstract

New Coordination Polymers Based On Transition Metal Squarates And Pyrazine Ligands

Abstract

Peri-Interactions in Naphthalenes, 9 [1]. On Hypercoordination in Non-Quaternary Phosphonium Salts and a Secondary Phosphine with the (8-Dimethylamino-Naphth-1-Yl) Substituent

Abstract

The Hexakis(N,N'-Dimethylurea)Cobalt(Ii) Cation: A Flexible Building Block for the Construction of Hydrogen Bonded Networks

Abstract

Abstract

Metallkomplexe mit Biologisch Wichtigen Liganden, CIL [1]. Metallorganische η2-N,O-Lysinato-Komplexe / Metal Complexes Of Biologically Important Ligands, Cil [1]. Organometallic η2-N,O-Lysinato-Complexes

Abstract

Synthese monofluorierter cyclopropanoider Nucleosidanaloga / Synthesis of Monofluorinated Cyclopropanoic Nucleoside Analogues

Abstract

Hydroxyurea Analogues of Fosmidomycin

Abstract

Synthesis of 2-Phenylisothiazol-3(2H)-One 1,1-Dioxides: Inhibitors of Human Leukocyte Elastase

Abstract

Erratum

The Reduction of Pyridine to 1,4-Dihydropyridine by Lithiumtetrahydroborate in the Presence of Water

Abstract

Preparation, Crystal and Magnetic Structure of the Double Perovskites Ca2TWO6 (T = Co, Ni)

Abstract

Hydroboration of Bis(Trimethylsilyl)Ethyne. New Aspects of Hydroboration

Abstract

Conductivity, Electrodeposition and Magnetic Property of Cobalt(II) and Dysprosium Chloride in Zinc Chloride-1-Ethyl-3-Methylimidazolium Chloride Room Temperature Molten Salt

Abstract

A Zwitterionic Platinum Complex with a Carbene Ligand

Abstract

Synthesis and Structural Characterization of the Mixed Ligand Complex [Cu(Hml)2(Phen)] · 2 H2O (H2ml = 2-Methyllactic Acid)

Abstract

Synthesis, Thermal and X-Ray Investigations of the High-Temperature Phase of Copper(I) Cyanide

Abstract

Rietveld Refinement of the Crystal Structure of α-Be3N2 and the Experimental Determination of Optical Band Gaps for Mg3N2, Ca3N2 and CaMg2N2

Abstract

Preparation and Crystal Structure of Hexapotassium-μ-Oxo-Hexathiodititanate(IV), K6Ti2OS6

Abstract

(Phosphine)Silver(I) Sulfonate Complexes

Abstract

Beryllium Dichloride Coordination by Nitrogen Donor Molecules

Abstract

Zur gezielten Synthese funktionell substituierter Oligosilane aus Silyltriflaten und Aminosilyllithiumverbindungen / Tailor-Made Synthesis of Functional Substituted Oligosilanes from Silyl Triflates and (Aminosilyl)Lithium Compounds

Abstract

Secondary Bonding Interactionsi in Some Di- and Trihaloanilinium Halides

Abstract

Ba9[NbN4]2O[Cn2] – Synthesis, Crystal Structure and Raman Spectrum

Abstract

Dinuclear Derivatives of Mn₂(CO)₁₀ with the Ligand Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane, P(C₇H₇)₃, and their Oxidative Cleavage

Synthesis and Reactivity of Bromo-Mer-Tricarbonyl-Trans-Bis[Tri(1-Cyclohepta- 2,4,6-Trienyl)Phosphane]-Manganese, Mnbr(CO)₃[P(C₇H₇)₃]₂

Transition Metal-Gallium Ordering In HfCoGa2 And HfNiGa₂

Tungstenmethyl-Dimethylsilanols Cp(Oc)₂(R₃P)W—CH₂—SiMe₂OH (R = Me, Ph) – Synthesis Via Oxygenation or Hydrolysis

Metallkomplexe mit Biologisch Wichtigen Liganden, CIL [1]. Metallorganische η²-N,O-Lysinato-Komplexe / Metal Complexes Of Biologically Important Ligands, Cil [1]. Organometallic η²-N,O-Lysinato-Complexes

Preparation, Crystal and Magnetic Structure of the Double Perovskites Ca₂TWO₆ (T = Co, Ni)

Synthesis and Structural Characterization of the Mixed Ligand Complex [Cu(Hml)₂(Phen)] · 2 H₂O (H₂ml = 2-Methyllactic Acid)

Rietveld Refinement of the Crystal Structure of α-Be₃N₂ and the Experimental Determination of Optical Band Gaps for Mg₃N₂, Ca₃N₂ and CaMg₂N₂

Preparation and Crystal Structure of Hexapotassium-μ-Oxo-Hexathiodititanate(IV), K₆Ti₂OS₆

Ba₉[NbN₄]₂O[Cn₂] – Synthesis, Crystal Structure and Raman Spectrum