bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kristallstrukturen, Schwingungsspektren und Normalkoordinaten- analysen von trans-[OsO2(ox)2]2– und trans-[OsO2(mal)2]2–/ Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of trans-[OsO2(ox)2]2– and trans -[OsO2(mal)2]2–
Authors: Strueß A. , Preetz W. 
Published: February 2015

Abstract
The crystal structures of trans-(Ph4P)2[OsO2(ox)2] (monoclinic, space group P21/n, a = 12.281(2), b = 14.5440(13), c = 13.9810(12) Å, β = 100.000(8)°, Z = 2) and trans- (n-Bu4N)2[OsO2(mal)2] (triclinic, space group P1̄, a = 10.365(4),b = 10.707(3), c - 11.473(5) A, a = 73.00(2), β = 64.44(3), 7 = 82.55(3)°, Z = 1) have been determined by single crystal X-ray diffraction analysis. The IR and Raman spectra of these complexes were measured at room temperature. Based on the molecular parameters of the X-ray determinations normal coordinate analyses have been performed and the vibrations assigned. The valence force constants of [OsO2(ox)2]2- are fd(Os=O) = 6.7, fd(Os-O) = 2.9, fd(C-O) = 5.05, fd(C=O) = 11.2 and fd(C-C) = 4.7 mdyn/Å and of [OsO2(mal)2]2- fd(Os=O) = 6.7, fd(Os-O) = 2.9, fd(C-O) = 4.86, fd(C=O) =11.1 and fd(C-C) = 4.07 mdyn/Å.
Photooxidation of Dicyanoaurate(I) Induced by Metal-to-Ligand Charge Transfer Excitation
Authors: Kunkely Horst , Vogler Arad 
Published: February 2015

Abstract
The irradiation of [Au(CN)2]- in oxygen-saturated acetonitrile leads to photooxidation of Au(I). In the presence of additional chloride [Au(CN)2CL2]- is formed with φ= 0.5 x 10-4 at λirr = 254 nm. It is assumed that [Au(CN)2]- in its metal-to-ligand charge transfer state undergoes an excited state electron transfer to oxygen in the primary photochemical step.
Halogeno(acylphenolato)cobalt(III)-Verbindungen mit Trimethylphosphan-Liganden/ Halogeno(acylphenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands
Authors: Klein Hans-Friedrich , Haller Stefan , Sun Hongjian , Li Xiaoyan , Jung Thomas , Röhr Caroline , Flörke Ulrich , Haupt Hans-Jürgen 
Published: February 2015

Abstract
Complexes mer-CoH(CO-CR=CR′-O)(PMe3)3 react with haloalkanes RX (X = Br, I) or with acids HX (X = Cl, Br) under elimination of dihydrogen. In both reactions a change of configu­ration at the metal is brought about by directional steering through the hard/soft (acyl)enolato chelate ligands to form octahedral complexes mer-CoX(CO-CR=CR′-C))(PMe3)3 or sterically crowded ionic compounds [Co(CO-CR=CR′-O)(PMe3)4(3)]+ X-(X = ClO4) without opening of the (acyl)enolato chelate ring.
Crystal Structure and Spectroscopic Behaviour of a Binuclear Copper(II) Complex of Mefenamic Acid and Dimethylsulfoxide
Authors: Facchin G. , Torre M. H. , Kremer E. , Piro O. E. , Baran E. J. 
Published: February 2015

Abstract
The crystal structure of the binuclear Cu(II) complex [Cu(mef)2DMSO]2 (mef = deprotonated N-2,3-dimethylphenyl-anthranilic acid; DMSO = dimethylsulfoxide) has been determined by single-crystal X-ray diffractometry. It crystallizes in the triclinic space group P1̄ with Z = 1. IR and electronic spectra of the compound are also discussed briefly.
Zur Reaktion von 2,3-Dihydroimidazol-2-ylidenen mit Pentafluorpyridin: Carbene als Reaktionspartner in der nucleophilen aromatischen Substitution/ On the Reaction of 2,3-Dihydroimidazol-2-ylidenes with Pentafluoropyridine: Carbenes as Reactants in Nucleophilic Aromatic Substitution
Authors: Kuhn Norbert , Fahl Joanna , Boese Roland , Henkel Gerald 
Published: February 2015

Abstract
The 2,3-dihydro-1,3,4,5-tetraalkylimidazol-2-ylidenes 3 (R = Me, iso-Pr) react immediately with pentafluoropyridine to form the 2-tetrafluoropyridylimidazolium salts 4 in good yields. In contrast with the tetramethyl derivative 4a, alkyl fluoride is eliminated from the isopropyl salt 4b to give 1 -isopropyl-4,5-dimethyl-2-tetrafluoropyridylimidazole, which dimerises via hydrogen bridges in the solid state (7). The X-ray structures of 1,3-diisopropyl-4,5-dimethyl-2-tetrafluoropyridylimidazolium chloride (5) and 7 are reported.
Synthesis of Some Chromanone Derivatives and the Use of DNA in Evaluation of their Biological Activity
Authors: El-Desoky El-Sayed I. , El-Telbani Emad. M. , Hammad Mahmoud A. 
Published: February 2015

Abstract
6-Formyl-7-hydroxy-5-methoxy-2-pentamethylenechromanone (2) was prepared from the naturally occurring “Visnagin” and condensed with benzil, o-phenylenediamine and 3,4-diaminobenzophenone to give the corresponding imidazolylchromanone derivatives 3-5. Knoevenagel reaction of compound 2 with different active methylene compounds afforded benzodipyranone derivatives 12a - c which may be considered as analogues to the naturally occurring “Xanthyletin and Graveolone Compounds”. The structural formula of the new compounds were established by using different methods for their preparation in addition to the instrumental analyses. Some compounds in this study were biologically evaluated for their ability to bind to DNA.
[R2S-CH2-OTf]+ OTf– as a Reagent with an Optionally Mono-or Biselectrophilic Csp3 Center
Authors: Weiss Robert , Handke Matthias , Hampel Frank 
Published: February 2015

Abstract
Sulfonium salts [R2S-CH2-OTf]+ OTf- 1a,b are synthetically versatile 1,1-biselectrophiles featuring the sulfonio- and triflato-substituents as leaving groups of differential nucleofugic power. Reactions with a number of neutral nucleophiles |Nu yield a series of novel sulfoniom ethylated onium salts [R2S-CH2-Nu]2+ 2OTf- 2 - 8 under very mild conditions. Structures of salts 2a, 5a and 6b were confirm ed by X -ray analysis. With certain N -hetarenes exchange of both nucleofuges in la was achieved, yielding the symmetrical 1,1-bisonium salts 9 and 10. With pyridine(derivatives) selective substitution of the sulfoniofunction in 1,1-bisonium systems 2a and 5a was also realized. These reactions represent typical examples of nucleophilic substitutions at geminally bisonio substituted Csp3 centers, which we recently have introduced as a novel variant of Sɴ2 reactivity.
Notizen: Preparation, Structures and Optical Properties of [H3N(CH2)6NH3]BiX5 (X=I, Cl) and [H3N(CH2)6NH3]SbX5 (X=I, Br)
Authors: Mousdis G. A. , Papavassiliou G. C. , Terzis A. , Raptopoulou C. P. 
Published: February 2015

Abstract
The preparation, crystal structures and optical absorption spectra of [H3N(CH2)6NH3]BiX5 (X= I, Cl) and [H3N(CH2)6NH3]SbX5 (X =I, Br) are reported. The anions of the compounds consist of MX6-octahedra (M =Bi, Sb) sharing cisvertices in one-dimensional zig-zag chains. Because of their one-dimensional character, a blue shift of the excitonic absorption bands, in com parison to those of higher dim ensionality systems (MX3), is observed.
Notizen: Die Kristallstruktur von ClPb[N(SiMe3)2]3 / Crystal Structure of ClPb[N(SiMe3)2]3
Authors: Smith Donna M. , Neumüller Bernhard , Dehnicke Kurt 
Published: February 2015

Abstract
Pale brown single crystals of the title compound have been obtained by the reaction of Pb[N(SiMe3)2]2 with molybdenum pentachloride in ether solution as a result of a redox reaction. ClPb[N(SiMe3)2]3 crystallizes in the trigonal space group R3 with three formula units per unit cell. Lattice dimensions at -50 °C: a = b -1828.7(2), c = 854.5(1) pm. The compound forms monomeric molecules with bond lengths Pb-Cl = 247.9(4) pm and Pb - N = 213(2) pm.
Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LIX [1], Ein Addukt des Me3P-substituierten Ferrio-diphenylphosphans Cp(OC)(Me3P)Fe-PPh2 mit Methylisothiocyanat: Darstellung, Protonierung und Methylierung / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LIX [1]. An Adduct of the Me3P-Substituted Ferrio-diphenylphosphane Cp(OC)(Me3P)Fe-PPh2 and Methylisothiocyanate: Synthesis, Protonation, and Methylation
Authors: Malisch Wolfgang , Spörl Andre , Thirase Katharina , Fey Oliver 
Published: February 2015

Abstract
Treatment of the ferrio-phosphane Cp(OC)2Fe-PPh2 (1) with Me3P (2) yields Cp(OC)(Me3P)Fe-PPh2 (3) via CO-substitution. Reaction of 3 with methylisothiocyanate (4) leads to the formation of the adduct Cp(OC)(Me3P)Fe-PPh2 -C(S)NMe (5), which is regioselectively methylated at the sulfur atom with Mel (6a) or MeSO3CF3 (6b), respectively, to give the cationic complexes [Cp(OC)(Me3P)Fe-PPh2 -C(SMe)=NMe]I/CF3 SO3(7a,b). In contrast, protonation with CF3SO3H (8 ) occurs at the nitrogen atom, yielding [Cp(OC)(Me3P)Fe-PPh2- C(S)-N(H)Me]CF3SO3 (9). The structures of 7b and 9 have been determined by X-ray diffraction analysis
Phosphenium-Komplexe, 43 [1]. Ringöffnungsreaktionen der dreigliedrigen Phosphametallacyclen {PR2 = P(o-Tol)2, P(Ph)(o-Tol), P(Mes)[C(S)N(H)Et], P(/-Bu)[C(O)N(H)Et} / Phosphenium Complexes, 43 [1]. Ring-Opening Reactions of the Three-Membered Phosphametallacycles {PR1 = P(o-Tol)2, P(Ph)(oTol), P(Mes)[C(S)N(H)Et], P(r-Bu)[C(0)N(H)Et}
Authors: Malisch Wolfgang , El Baky Christa Abd , Grün Klaus 
Published: February 2015

Abstract
The three-membered phosphametallacycles

[R = o-Tol (3a), R = Ph(3b)] react with the tertiary phosphanes Me3P (4a), Me2PhP (4b) or MePh2P (4c) with ring opening and deselenation to the metallo-phosphanes fran.s-Cp(OC)2(R3P)WP(o-Tol)(R) (5a-d). Analogous reactions of the P-thioformamido- and formamido-substituted metallacycles

[R = Mes, X = S (6a); R = t-Bu, X = O (6b)] with Me3P (4a) yield in the case of 6a the tungsten-phosphane Cp(OC)2(Me3P)W-P(Mes)[C(S)N(H)Et] (7), while 6b affords the tungsten-selenophosphorane Cp(OC)2(Me3P)W-P(Se)(f-Bu)[C(0)N(H)Et] (8 ). Treatment of 7 with hydrogen chloride affords {Cp(OC)2(Me3P)W-P(H)(Mes)[C(S)N(H)Et] }C1 (9). With methyliodide, 8 is transformed into {Cp(OC)2(Me3P)W-P(SeMe)(t-Bu)[C(O)N(H)Et]}I (10)
Synthese, Kristallstruktur und Eigenschaften von Triguanidinium-tri--imidocyclotriphosphat-Monohydrat und Tetraguanidinium-tetra-/i-imidocyclotetraphosphat-Tetrahydrat, [C(NH2)3]3(PO2NH)3 · H2O und [C(NH2)3]4(PO2NH)4 · 4 H2O / Synthesis, Crystal Structure, and Properties of Triguanidinium Tri-/i-imidocyclotriphosphate Monohydrate and Tetraguanidinium Tetra-/i-imidocyclotetraphosphate Tetrahydrate, [C(NH2)3]3(PO2NH)3 · H2O and [C(NH2)3]4(PO*NH)4 · 4 H2O
Authors: Stock Norbert , Jürgens Barbara , Schnick Wolfgang 
Published: February 2015

Abstract
Coarsely crystalline [C(NH2)3]3(PO2NH)3 · H2O (1) and [C(NH2)3]4(PO2NH)4 · 4 H2O (2) have been obtained by addition of [C(NH2)3]2CO3 to a freshly prepared solution of H3(PO2NH)3 or to a suspension of H4(PO2NH)4 · 2 H2O , respectively, followed by diffusion controlled addition of acetone. The crystal structures of 1 and 2 have been determined by single crystal X-ray methods ([C(NH,)3]3(PO,NH)3 · H2O: Pbca; a = 1565.6(2), b = 1068.31(6), c = 2091.8(2) pm, Z = 8; [C(NH2)3]4(PO2NH)4 · 4 H2O: Pbcn; a = 1739.64(10), b = 1084.19(6), c = 1334.96(11) pm, Z = 4). The P3N3 and P4N4 rings of the anions exhibit the chair conformation. In 1 two cyclic anions are interconnected into pairs via hydrogen bonds. In 2 columns along [001] are formed by hydrogen bonds between the anions. Hydrogen bonding through water molecules and C(NH2)3
+ ions results in a three-dimensional network in 2. Complete dehydration is achieved below 160 or 180 °C for 1 or 2, respectively. Heating to 700 °C causes condensation reactions with evolution of NH3 and H2O yielding X-ray amorphous products
Niedere Hydrate aliphatischer primärer Amine. Neue Untersuchungen zu Bildung und Struktur [1] / Lower Hydrates of Aliphatic Primary Amines. New Studies of Formation and Structure [1]
Authors: Janeda Stephanie , Mootz Dietrich 
Published: February 2015

Abstract
After earlier work in this laboratory on lower hydrates of amines, the melting diagram of the system 1,8-diaminooctane/water and six new crystal structures of hemi- and monohydrates of terminal primary n-alkylamines and diamines have been determined. In the hydrates 1 -PrNH2 · 0.5 H2O (space group C 2/m with Z = 4 formula units per unit cell), l-HexNH2 · 0.5 H2O (PI, Z = 2) and H2N(CH2)nNH2 · H2O with n = 4, 6, 8 (P 2x/c, Z = 4), the O and N atoms are hydrogen-bonded into a two-dimensional array analogous to the mutual coordination of cations and anions in the Cdl2 structure type: [ON6/3] ~ [CdI6/3]. In the hydrate H2N(CH2)2NH2 · H2O (C 2/c, Z = 4), the H2O/NH2 partial structure is three-dimensional but can be reduced, by neglecting the longest H bond, to an array which is again just two-dimensional and related now to the red Hgl2 structure type: [ON4/2] ~ [HgI4/2], In all the monohydrates, the arrays as defined are crosslinked by the alkylene cnains of the bifunctional amine molecules
Synthesis and Thermal Properties of Twin Compounds, Alkanediacids 4-(4'-Cyano)-biphenyl Diesters
Authors: Białecka-Florjańczyk Ewa , Wolarz Eryk , Bauman Danuta 
Published: February 2015

Abstract
Alkanediacids 4-(4'-Cyano)-biphenyl Diesters, Twin M esogens Four twin mesogens from the hom ologous series of alkanediacids 4-(4'-cyano)-biphenyl diesters (n = 4, 6, 8, 10) have been synthesized and their thermal properties have been studied. Assignment of the phases has been made by means o f polarizing microscopy and DSC measurements. It has been found, that the increase of the spacer length causes the lowering of the mesophase temperature range and influences other thermodynamic parame­ ters of the compounds investigated.
Ab initio MO Optimizations of Osmiumtetracarbonyldihydride and Metallacyclophanes with two Osmium Atoms and their Molecular Complexes with Different Guests
Authors: Warttmann Inge , Häfelinger Günter 
Published: February 2015

Abstract
Ab initio Hartree-Fock (HF) and density functional (DFT) optimizations on the test m olecule osmiumtetracarbonyldihydride (13) with various basis sets show that the lanl2mb pseudopotential basis set for osmium leads in the HF approximation to more reliable molecular geometries than the DFT calculations. This HF procedure was used for the optimizations of molecular geometries of three isomeric 4,4,4,4,17,17,17,17-octacarbonyl-4,17-diosma[7.7]ortho-, meta- and paracyclophanes 1 to 3, of which 3 was found to be predestined for formation of various host-guest complexes with possible guests benzene (4), fluorobenzene (5), 1,3,5- trifluorobenzene (6), 1,2,4,5-tetrafluorobenzene (7), hexafluorobenzene (8), fluoroanil (9), tetrafluoroethene (10), tetracyanoethene (11) and aniline (12). Results of optimized hostguest geometries are presented graphically for inclusions and associations of guest 4 to 12 with 3. Calculated lanl2mb interaction energies, after correction for basis set superposition error (BSSE), remain favourable only for inclusion of 5 and associations of 5, 10, 11 and 12. Additionally lanl2dz single point calculations for inclusion, which may not need BSSE correction because of the improved basis set, are favourable for 6 and 12. According to lanl2mb HOMO and LUMO energies, 3 may as well easily donate or accept electrons. This may be an interpretation to the surprising effect, that Mulliken total charges are positive on the electron accepting guest molecules 4 to 11. There are geometrical peculiarities in the optimized host-guest complexes for inclusion and association. Fluorine atoms of 5 to 10 and nitrogen atoms of a cyano group of 11 and the amino group of 12 like to come close to one or two carbonyl groups. Similar distances of 2.70 Å to 3.57 Å between the O atom of the carbonyl group and the F atom or N atom appear in all optimizations of inclusion and association of 5 to 12 except in the case of association of tetrafluoroethene (10).
Kristallstruktur des Oxo-Acetatkomplexes [Co7(μ4- O)2(O2CCH3)10(OPEt3)2] / Crystal Structure of the Oxo-Acetate Complex [Co7(μ4 -O)2(O2CCH3)10(OPEt3)2]
Authors: Ackermann Hartmut , Leo Roland , Massa Werner , Dehnicke Kurt 
Published: February 2015

Abstract
Cobalt(II)acetate reacts with the silylated phosphinimine Me3SiNPEt3 at 230 °C to form a reaction mixture from which dark blue single crystals have been isolated by recrystallization from dichloromethane/ acetonitrile. They were identified by a crystal structure determination to be [Co7(μ4- O)2(O2CCH3)10(OPEt3)2] · 4 CH3CN (1). Lattice dimensions at 190 K: a = 1048.9(1), b = 1217.5(1), c = 1280.6(1) pm, a = 87.75(1)°, β = 77.72(1)°, y = 73.90(1)°, space group P1, Z = 1, R1 = 0.0257. 1 has a centrosymmetric cluster-like structure in which the central cobalt atom is connected via two μ4-oxygen atoms with the remaining six cobalt atoms to form a distorted Co(Co)6 octahedral skeleton. In addition, all cobalt atoms are linked by six ,μ2- O2CCH3
- groups and by four μ3-OC(O)CH3
- bridges
Thermochemisches und kalorisches Verhalten von NdAl3Cl12 / Thermochemical and Calorical Behaviour of NdAl3Cl12
Authors: Oppermann H. , Zhang M. , Hennig C. 
Published: February 2015

The thermodynamical data of solid and gaseous aluminium neodymium chloride have been obtained by determination of the decomposition equilibria (of solid) from total pressure measurements and chemical transport reactions (gaseous). The melting diagram was determined by DTA. The enthalpy of formation of the solid phase was calculated from their heats of solution and from the enthalpies of formation and the heats of solution of NdCl3 and AlCl3.
Data by total pressure measurement:
ΔH°B |(NdAl3Cl12,f,298) = -749,6 ± 2,5 kcal/mol; S°(NdAl3Cl12,f,298) = 118,2 ± 3,0 cal/K·mol.
Data by solution calorimetry: ΔH°B(NdAl3Cl12,f,298) = -748,6 ± 1,3 kcal/mol.
Data by chemical transport:
ΔH°B(NdAl3Cl12,g,298) = -701,5 ± 3,0 kcal/mol; S°(NdAl3Cl12,g,298) = 215,0 ± 4,0 cal/K-mol.
Oligomere Tetraeder-Anionen in Borophosphaten: Sechserringe mit offenen und cyclischen Phosphat-Verzweigungen in der Kristallstruktur von K6Cu2[B4P8O28(OH)6] / Oligomeric Tetrahedral Anions in Borophosphates: Six-Membered Rings with Open and Cyclic Phosphate Branchings in the Crystal Structure of K6Cu2[B4P8O28(OH)6]
Authors: Boy Insan , Cordier Gerhard , Kniep Rüdiger 
Published: February 2015

Abstract
Crystals of K6Cu2[B4PhO28(OH)6] were grown under hydrothermal conditions at 160 °C. The crystal structure (monochnic, P21/c (Nr. 14), a = 961.8(1), b = 1755.0(1), c = 942.0(1) pm, β = 112.29(1)°, Z = 2) contains oligomeric tetrahedral anions based on six-membered rings {B4P2O10O8/2} with additional branchings by hydrogenphosphate-groups (open branching: 4 x HPO3O1/2; cyclic branching: 2 x HPO2O2/2). The complex borophosphate anion is represented by the formula [B4P8O28(OH)6]10-. Cu2+ is in a tetragonal pyramidal and K+ in an irregular coordination by eight and nine oxygen ligands, respectively.
Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer FeII-Komplexe mit [FeN2S2]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New FeII Complexes with [Fe2N2S2] Cores
Authors: Sellmann Dieter , Emig Susanne , Heinemann Frank W. , Knoch Falk 
Published: February 2015

Abstract
In order to obtain suitable precursors for iron complexes that model the reactivity of the active sites of nitrogenases, the coordination chemistry of the [Fe(′N2H2S2′)] fragment was systematically investigated(′N2H2S2′2- = 1,2-ethanediamine-N,N′-bis(2-benzenethiolate)(2-)). One-pot reactions of FeCl2 -4H2O with the tetradentate amine-thiolate ligand ′N2H2S2′2- and CO, PR3 or P(OR)3 yielded the complexes [Fe(CO)2(′N2H2S2′)] (1), [Fe(CO)(PR3)(′N2H2S2′)] (R = Et (2), Pr (3), Bu (4)), [Fe(PMe3)2 (′N2H2S2′)] (7), [Fe(dppe)(′N2H2S2′)] (8 , dppe = 1,2- bis(diphenylphosphine)ethane), and [Fe(P(ÖR)3)2(′N2H2S2′)l (R = Me (9), Pr (10)). Mixed phosphane/phosphite complexes [Fe(PMe3)(P(OR)3)(′N2H2S2′)] (R = Me (11), Pr (12)) were synthesized by PMe3/P(OPr)3 exchange of the labile complexes [Fe(PMe3 )2(′N2H2S2′)] (7) and [Fe(P(OPr)3)2(′N2H2S2′)] (10). The [Fe(CO)(PR3)(′N2H2S2′)l complexes 3 and 4 also resulted from 1 and PR3 by photochemical CO substitution. They exhibit characteristic low-frequency v (CO) bands ( ≈1925 cm-1), and their remaining CO ligand proved photolytically inert. Reaction of 3 or 4 with NOBF4 yielded the dinuclear NO complex [Fe(NO)(′N2HS2′)]2 (6 ) which contains two amide functions.
Contrary to expectations, [Fe(PR3)2(′N2H2S2′)l complexes could not be obtained with monodentate phosphanes other than PMe3. The corresponding N-methylated ligand ′N2Me2S2,2- yielded only the complexes [Fe(CO)2 (′N2Me2S2′)] (15) and [Fe(′N2Me2S2′)] (16). X-ray structure analyses of complexes 7, 8 -MeOH, 3, [Fe(CO)(dppm)(′N2H2S2 ′)]·0,5 THF (5 ·0,5THF, dppm = bis(diphenylphosphino)methane), and 12·0,5′N2 H2S2 ′-H2 confirm the pseudo-octahedral coordination of the Fe centers by two trans-S and two cis-N donors and two c/s-coligands. The structural data further suggest that the unexpected instability of the [Fe(PR3)2 (′N1H2S2′)] complexes is not caused by steric but by electronic effects. The cyclic voltammograms and the reactivity of the [Fe(L)(L′)(′N2H2S2′)] complexes corroborate this assumption. The oxidation behaviour of the [Fe(L)(L′)(′N2H2S2′)] complexes depends critically on the coligands L and L′. Reaction of 1 with dioxygen leads to oxidative dehydrogenation of the ′N2H2S2′2- ligand and yields the dinuclear Schiff-Base complex [Fe(′gma′ )]2 (′gma′2- = glyoxal-bis(2- mercaptoanil)(2-)). In contrast, oxidation of [Fe(CO)(PR3)(′N2H2S2′)], [Fe(PR3)2 (′N2H2S2′)] and [Fe(P(OR)3)2 (′N2H2S2)] complexes by dioxygen occurs metal-centered and gives the Fe(IV) complexes [Fe(PR3)(′N2S2′)] (R = Me, Pr), [Fe(P(OR)3)(′N2S2′)] (R = Me) and [Fe(′N2S2′)]2 that contain the tetraanionic thiolate-amide ligand ′N2S2′4-.
BaCu6Ge2S8 -Ein Thiogermanat als Variante der Li3Bi-Struktur / BaCu6Ge2S8 -A Thiogermanate as a Variant of the Li3Bi Structure
Authors: Tampier Markus , Johrendt Dirk 
Published: February 2015

Abstract
BaCu6Ge2 S8 was synthesized by direct reaction of the elements at 750°C and characterized by X-ray single crystal techniques. The thiogermanate crystallizes in a new orthorhombic structure type (a = 6.122(1) Å, b = 12.084(3) Å, c = 17.614(5) Å; Pbcm, Z = 4). Isolated [GeS4]4- tetrahedra form a slightly distorted cubic face-centered (fee) arrangement. Baand Cu-atoms each occupy half the octahedral gaps (OG) of this “tetrahedra packing” . Further Cu atoms fill the tetrahedral gaps ( TG) completely. The compound can be written as Ba2
(1/2OG)(Cu2)2
(1/2OG)Cu8
(TG)(GeS4)4 . Thus the structure of BaCu6Ge2S8 can be derived from the Li3Bi type. The sulfur coordination of the metal atoms (Cu tetrahedral or trigonal, Ba with CN 8) are realized by the spatial orientation of the [GeS4]4- tetrahedra. Their centers nearly maintain the fcc-arrangement. This structure interpretation of BaCu6 Ge2S8 from the viewpoint of a “filled tetrahedra packing” is discussed for further known thiogermanate compounds.
Molecular Recognition Analyzed by Observing Intramolecular Interconversion with EPR Spectroscopy
Authors: Jäger Martin , Schuler Paul , Stegmann Hartmut B. , Rockenbauer Antal 
Published: February 2015

Abstract
Molecular recognition between Rebek’s cleft R and 4-(2-benzimidazolyl)-aminomethyl-2,6-di-rm-butyl-phenol (Bi) is investigated by means of EPR spectroscopy. Their specific inter-molecular interactions are distinguished from non-specific interactions represented by mere protonation on addition of benzoic acid. Both interactions are related to intramolecular in­ terconversions at the C∞-atom of Bi*, where a two-jump mechanism is found for free and protonated Bi* and a two-site exchange for the complexed ligand. While NMR spectroscopy indicates the existence of 1:1 and 1:2 receptor-substrate complexes, the faster time scale of EPR spectroscopy allows to identify one 1 : 2 as well as three 1 : 1 associates and to elucidate their formation conditions. Based upon the corresponding hf parameters, binding modes and sites are proposed for the key-in-the-lock system.