bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthese und Kristallstruktur von N,N′-Bis(trimethylsilyl)benzamidinato-dichlorogold, Ph— C(NSiMe3)2AuCl2 / Synthesis and Crystal Structure of N,N′-Bis(trimethylsilyl)benzamidinato-dichlorogold, Ph — C(NSiMe3)2AuCl2
Authors: Hiller Wolfgang , Strähle Joachim , Zinn Alfred , Dehnicke Kurt 
Published: March 2015

Ph—C(NSiMe3)2AuCl2 has been prepared by the reaction of N,N,N′-tris(trimethylsilyl)-benzamidine with AuCl3 in CH2Cl2 suspension, forming orange-red crystals, which were characterized by an X-ray structure determination.
Space group P21/n, Z = 4, 2358 observed independent reflexions, R = 0.028. Lattice dimensions (20°C): a = 695.9(3); b = 1576.1(3); c = 1830.9(3) pm; β = 94.27(3)°. The compound forms monomeric molecules, in which the gold atom is in a square planar arrangement of the two nitrogen atoms of the benzamidinato chelate (Au—N 201.6(7); 203.3(6) pm) and by two chlorine atoms (Au—Cl 227.9(3); 228.5(2) pm).
Synthese und Kristallstruktur des Imidokomplexes {TaCl4NC(Ph)[N(SiMe3)2]}2 · 2 CH2Cl2 / Synthesis and Crystal Structure of the Imido Complex {TaCl4NC(Ph)[N(SiMe3)2]}2 · 2 CH2Cl2
Authors: Merzweiler Kurt , Fenske Dieter , Hartmann Eva , Dehnicke Kurt 
Published: March 2015

The title compound has been prepared by the reaction of N,N,N′-tris(trimethylsilyl)benzamidine with tantalum pentachloride in CH2Cl2 suspension, forming amber-coloured, moisturesensitive crystals, which were characterized by an X-ray structure determination. Space group P 21/n, Z = 2, 4895 observed independent reflexions, R = 0.059. Lattice dimensions (-65°C): a = 1165.2(6), b = 1335.4(6), c = 1629.0(7) pm, β = 93.23(4)°. The complex forms centrosymmetric molecules dimerized via chloro bridges TaCl2Ta with TaCl bond lengths of 247.2(2) and 277.1(2) pm, the longer one being in trans-position to the imido group, which can be formulated
as [xxx] (bond lengths Ta=Ν = 183.5(8), C=N = 134(1) pm, bond angle TaNC = 162.7(7)°).
Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, XXIV [1]. Rhodium-Komplexe mit (Ether-Phosphan)-Liganden unterschiedlicher Basizität und ihr Einfluß bei der Methylwanderung / Novel Basic Ligands for the Homogenous Catalytic Methanol Carbonylation, XXIV [1]. Rhodium Complexes with (Ether-Phosphane) Ligands of Different Basicity and their Influence on the Methyl Migration
Authors: Lindner Ekkehard , Norz Hubert 
Published: March 2015

[(COD)Rh(Cl)(P1∼O)] (3) is obtained from [µ-ClRh(COD)]2 (1) and the (ether-phosphane) ligand P1∼O (2) [P1∼O = Ph2PCH2CH2OCH3]. 3 reacts with AgSbF6 to form the cationic η2-Pl͡ O rhodium complex [(COD)Rh(P1 ͡ O)][SbF6] (4). Addition of another ligand P2∼O (5) [P2∼O = Pr2PCH2C4H7O] to 4 affords the bis(ether-phosphane)rhodium complex
[(COD)Rh(P1∼O)(P2∼O)][SbF6] (6) with two different ether-phosphanes. In 6 COD is displaced by CO to give [trans-(P1∼O)(P2∼O)Rh(CO)3][SbF6] (7). The 31Ρ{1H} NMR spectrum of 7 shows a temperature dependence. When a THF solution of compound 7 is flushed with argon it undergoes elimination of carbon monoxide to form [trans-(P1∼O)(P2 ͡ O)Rh(CO)][SbF6] (10), containing a bidentate coordinated P2∼O ligand (5). The reaction is reversible. Oxidative addition of CH3I to 10 results in the formation of a 1:1 mixture of the acyl complexes [cis-(P1 ͡ O)(P2͡ O)Rh(I)(C(0)CH3)][SbF6] (8) and [cis-(P1͡ O)(P2͡ O)Rh(I)(C(O)CH3)][SbF6] (9), the reactive intermediate [trans-(P1∼O)(P2͡ O)Rh(I)(CH3)(CO)][SbF6] (11) not being observed. Formation of either 8 or 9 depends on the S or R configuration of the asymmetric C-atom in 5. On cleaving one or two Rh–O bonds the back reaction to 7 occurs.
Synthese und Kristallstruktur von PPh4[ReF2Cl2(N2S2)] / Synthesis and Crystal Structure of PPh4[ReF2Cl2(N2S2)]
Authors: Vogler Stefan , Dehnicke Kurt , Hiller Wolfgang 
Published: March 2015

PPh4[ReF2Cl2(N2S2)] has been prepared by the reaction of PPh4[ReCl4(NSCl)2] · CH2Cl2 with sodium fluoride in acetonitrile suspension. The compound forms black crystals, which were characterized by IR spectroscopy as well as by an X-ray structure determination.
Space group P21/c, Z = 4, 2525 observed unique reflexions, R = 0.053. Lattice dimensions at 20°C: a = 1277.4(3), b = 713.2(3), c = 2860.8(4) pm. β = 97.20(3)°. The compound consists of PPh4
+ and [ReF2Cl2(N2S2)]- ions, in which the rhenium atom is surrounded octahedrally by two fluorine atoms, two chlorine atoms, and by the nitrogen atoms of a ReN2S2 five-membered ring, the fluorine ligands being in trans position to the N atoms. The bond lengths ReN (172; 177 pm) and NS (155; 160 pm) are in the range of double bonds, the S—S bond is relatively long (243 pm).
Synthese und Reaktivität von Alkinyl-substituierten Titanocen-Komplexen / Synthesis and Reactivity of Alkyne Substituted Titanocene Complexes
Authors: Lang Heinrich , Seyferth Dietmar 
Published: March 2015

(η5-C5H5)2TiCl2 (1a) reacts with one equivalent of Li–C≡C–Si(CH3)3 to yield the mono alkynyl-substituted titanocene complex η5C5H5)2,Ti(Cl)[C≡C–Si(CH3)3] (2). The reaction of 2 with another equivalent of Li–C≡C–Si(CH3)3 gives the disubstituted compound (η5-C5H5)2Ti[C≡C–Si(CH3)3]2 (3f).
In general, complexes of the type (η5-C5H4R)2Ti(C≡C–R′)2 (R = H, CH3, Si(CH3)3; R′ = C6H5, C2H5, nC3H7, nC4H9, ′C4H9, Si(CH3)3), 3-5, can be prepared by the reaction of η5-C5H4R)2,TiCl2 (1) and two moles of E–C≡C–R′ (E = BrMg, Na, Li; R, R′ = see above) to give the compounds 3-5 in yields of up to 95%. The reaction of 2-5 with X2 or HX yields the appropriate compounds η5-C5H4R)2TiX2 (X = F, Cl, Br) and H–C≡C–R′ or X–C≡C–R′.
Hochdruckumwandlungen von Cer(III)Orthovanadat(V), CeVO4 / High-Pressure Transformations of Cerium(III) Orthovanadate(V), CeVO4
Authors: Range Klaus-Jürgen , Meister Helmut , Klement Ulrich 
Published: March 2015

The polymorphism of CeVO4 was investigated at high pressures and temperatures in a Belttype high-pressure apparatus. In addition to the normal-pressure modification CeVO4— I with zircon-type structure two high-pressure modifications have been found, viz. monazite-type CeVO4—II and scheelite-type CeVO4—III. CeVO4—II is stable between 1 bar and 30 kbar at 1300 °C. Its region of existence decreases rapidly at lower temperatures. From the observed p,T-relations for the I-II and I-III transformations a triple point CeVO4—I,II,III at about 27 kbar, 500 °C can be estimated. For kinetic reasons, however, the experimental determination of phase relations becomes difficult at temperatures below 600 °C.
The crystal structures of CeVO4— I and —II have been refined from single-crystal data. Crystallographic data for the three modifications are given and discussed (CeVO4—I: I 41/amd, a = 7.383(1)Å, c = 6.485(1)Å, Z = 4; CeVO4—II: P21/n, a = 7.003(1)Å, b = 7.227(1)Å, c = 6.685(1)Å, β = 105.13(1)°, Z = 4; CeVO4—III: I 41/α, a = 5.1645(2)Å, c = 11.8482(7)Å, Z = 4).
Breitlinien 185Re- und 187Re-Festkörper-NMR-Spektroskopie an Metaperrhenaten mit alkylsubstituierten Kationen der V. Hauptgruppe / Wideline 185Re and 187Re Solid-State NMR Spectroscopy of Metaperrhenates with Alkyl-Substituted Cations of Main Group V
Authors: Burkert Paul K. , Grommelt Meinhard , Pietraß Tanja , Lachmann Joachim , Müller Gerhard 
Published: March 2015

127I solid-state NMR spectra of metaperiodates with alkyl- or aryl-substituted cations of main group V yield second order quadrupole effects due to the distortion of the tetrahedra surrounding the iodine nuclei. In some cases the 127I quadrupole effects were found to become very small or even vanish. Thus the isomorphous metaperrhenates should also be accessible by 185Re, 187Re solid-state NMR. Owing to the very large quadrupole moments of the 185Re and 187Re isotopes, very small distortions or changes in dynamical effects can be detected in systems with such voluminous cations.
The solid-state NMR spectra of (CH3)4AsReO4 yield the calculated 185Re, 187Re second order quadrupole effects. These result from two kinds of differently distorted ReO4- tetrahedra. X-ray investigations and calculations based on a point charge model for (CH3)4SbReO4 manifest the inaccessibility of quadrupole effects by wideline solid-state NMR in a magnetic field of Bo = 4.698 Tesla.
Bestimmung von Oberflächenoxiden auf Rußen durch potentiometrische Direkttitration in nichtwäßrigen Lösungsmitteln / Determination of Surface Oxides on Carbon Blacks by Direct Potentiometric Titration in Non-Aqueous Solvents
Authors: Besenhard J. O. , Gansmann H. P. , Meyer H. 
Published: March 2015

An attempt is made to quantitatively determine acidic and basic surface oxides on carbon blacks and also to monitor their acid and base strength distribution by direct potentiometric titrations in non-aqueous media.
In contrast to direct titration procedures proposed so far, our method allows to distinguish clearly between several types of acidic surface oxides of different acid strength. This is mainly achieved by improvements of the non-aqueous titration media. The total contents of weakly and strongly acidic and also of basic oxides determined by this very fast method is comparable to results obtained by slow and laborious indirect titrations.
Heterocyclische Siebenring-Verbindungen, XXXV / Heterocyclic Seven-Membered Ring Compounds, XXXV
Authors: Hofmann Hans , Göttfert Christine , Gaube Helmut 
Published: March 2015

Thermodynamic Data, Heterocyclic Seven-Membered Ring Compounds
On heating in carbon tetrachloride or nitromethane the 5-methoxy-1-benzothiepines 1-4 isomerize to the corresponding thionaphtholes 5-8, whereas in cyclohexane from 1-4 the usual desulfuration products C arise. Kinetic and thermodynamic data have been estimated for the reactions 3 → 7 and 4 → 8. If the thermal rearrangement of 3 resp. 4 takes place in presence of cyclohexene sulphide, one gets the desulfuration products C also in carbon tetrachloride or nitromethane as solvent together with the equimolar amount of cyclohexene. This behaviour leads to the assumption of a S2-spezies as the primary elimination product of sulphur from the episulphide intermediate A.
Radiolysis of Tertiary Butyl Hydroperoxide in Aqueous Solution. Reductive Cleavage by the Solvated Electron, the Hydrogen Atom, and, in Particular, the Superoxide Radical Anion
Authors: Phulkar Shailesh , Rao Balijepalli Sethu Madhava , Schuchmann Heinz-Peter , Sonntag Clemens von 
Published: March 2015

The reactions of the solvated electron, the H atom, the OH radical and the superoxide radical anion with t-butylhydroperoxide (t-BuOOH) have been studied in aqueous solutions using γ-radiolysis and pulse radiolysis to generate these radicals.
The solvated electron reacts rapidly with t-BuOOH (k=5 × 109dm3mol-1 s-1) yielding t-BuO· and ·OH in a ratio of 4:1. The yield of t-BuO· has been determined by measuring its fragmentation product, acetone.
The H atom reacts more slowly with t-BuOOH (k=5 × 10 7 dm3 mol-1 s-1). There is very little H-abstraction from the methyl and the hydroperoxyl groups (about 3%), the main reaction again being the scission of the hydroperoxyl function with a branching ratio t-BuO·/·OH of about unity.
The OH radical reacts with t-BuOOH considerably more slowly (k=8 × 10 7 dm3 mol-1 s-1) than with t-butanol (k=5 × 108 dm3 mol-1 s-1) with an approximate preference of 8:1 of abstracting a methyl hydrogen over a hydroperoxyl hydrogen atom. The carbon-centered radical undergoes γ-cleavage (k ≈ 102 s-1) thereby reforming an OH radical. The resulting chain reaction is rather short (maximum yield G(2-methyl-1,2-epoxypropane), 26 × 10-7 mol J-1 at low dose rate) due to H-abstraction at the hydroperoxyl function of t-BuOOH by the OH radical.
The superoxide radical anion also reacts with t-BuOOH by cleaving the hydroperoxyl function. Its reactivity is, however, rather low (k=5 dm3 mol-1 s-1)
Position 10 is Critical for Antagonists of the Luteinizing Hormone-Releasing Hormone and for Inhibition of Ovulation in Rats
Authors: Feng Dong-Mei , Ljungqvist Anders , Hook William A. , Bowers Cyril Y. , Folkers Karl 
Published: March 2015

Eleven analogs of the luteinizing hormone-releasing hormone (LHRH) have been designed, synthesized, bioassayed and compared for antiovulatory activity (AOA) in rats. The emphasis of design was on analogs with D–Ala10, Sar10, D–Ser10, (desGly10, NHEt), D–Abu10, Gly10, and with substitutions in position 5, 6, and 8.
High antiovulatory activity was obtained with analogs having D– Ala in position 10. Four earlier analogs, 1, 4, 11 and 13, with D– Ala in position 10, showed 67-100% AOA at 0.25 μg in rats. Analog 1 showed 60% AOA at 0.125 μg. The replacement of D–Ala10 in analog 11 by Sar10 in analog 12, retained activity, 62% vs. 67% AOA at 0.25μg, 100% vs. 90% AOA at 0.5 μg. This analog with Sar10 was the only one that did not show substantial loss of activity upon replacement of D–Ala10.
A Convenient Solid-Support Procedure for the Synthesis of Symmetric Disulphides. The Configuration of Aromatic Carben Atoms in the 1,6-Methano[10]annulene Framework
Authors: Neidlein Richard , Constantinescu Take , Krieger Claus , Deigner H.-P. 
Published: March 2015

Treatment of organic thiocyanates with aluminium oxide, at room temperature, is found to afford a convenient procedure for the synthesis of symmetric disulphides, under mild conditions.
An X-ray structure analysis of meso-di-(1,6-methano[10]annulen-2-yl)-disulphide (2a) suggests an intermediate sp2—-sp3 hybridization state for the aromatic carbon atoms and a faceasymmetric electronic distribution in the annulene ring. Using reported atomic coordinates, a similar configuration is determined for the parent structure 7. A higher π-electron density on the exo face of the aromatic ring may account for the known syn,syn stereochemical course of electrophilic addition to 7, as well as for the high reactivity of this system towards electrophiles, in addition and in substitution reactions.
Über die Darstellung der (Chlorthio)sulfoniumsalze [(CH3)2SSSCl]+SbF6
-, [(CH3)2SSCl]+SbF6
- und des isomeren [(CH3)(Cl)S – SCH3]+SbCl6
- / On the Preparation of the (Chlorothio)sulfonium Salts [(CH3)2SSSCl]+SbF6-, [(CH3)2SSCl]+SbF6
- and the Isomer [(CH3)(Cl)S–SCH3]+SbCl6
-
Authors: Minkwitz Rolf , Kornath Andreas , Krause Renate , Preut Hans 
Published: March 2015

The preparation of the stable compounds [(CH3)2SSCl]+SbF6
- and [(CH3)2,SSSCl]+SbF6
- from [(CH3)2SH]+SbF6- and SCl2 and S2Cl2, resp., is reported.
The isomer [(CH3)(Cl)S–SCH3]+SbCl6
- is prepared from [SCl3]+SbCl6
- and CH3SH in the molar ratio 1:2. For this salt a crystal structure analysis was carried out (Space group P212121, Z = 4, a = 750.1(4), b = 1133.7(3), c = 1614.8(3) pm).
Über die Reaktion von C(NMe2)4 mit zweikernigen Übergangsmetallcarbonylen; Kristallstrukturen von [C(NMe2)3][Mn(CO)5] und [C(NMe2)3][Co(CO)4] / On the Reaction of C(NMe2)4 with Binuclear Transition Metal Carbonyls: Crystal Structures of [C(NMe2)3][Mn(CO)5] and [C(NMe2)3][Co(CO)4]
Authors: Petz Wolfgang , Weller Frank 
Published: March 2015

The reactions of C(NMe2)4 (1) with Mn2(CO)10 or Co2(CO)8 in THF yield
[C(NMe2)3][Co(CO)4] (3) and [C(NMe2)3][Mn(CO)5] (4), respectively. The compounds Co(CO)4NMe2 (5) and Mn(CO)5NMe2 (6) could not be found. With CH2Cl2 4 is quantitatively converted into [C(NMe2)3][Mn(CO)4Cl2] (7) as shown by IR and 13C NMR investigations. 3 and 4 were characterized by an X-ray structure determination. 3: Space group Pnma, Z = 4, a = 7.435(2), b = 10.79(2), c = 20.299(5)Å. 4: Space group C2/c, Z = 4, a = 11.378(2), b = 10.165(1), c = 14.533(1) Å; β = 103.37(1)°. The compounds form independent ions with no bonding interactions between cation and anion; the central CN3 unit of the [C(NMe2)3]+ cation in 3 and 4 is disordered.
Niob-Stickstoff-Verbindungen: Synthese und Struktur der Halbsandwichkomplexe Ph3P = N–Nb(η5-C5EtMe4)Cl3 und [(η5-C5EtMe4)Cl3Nb–N = PPh2]2C2H2 / Niobium Nitrogen Complexes: Synthesis and Structure of Halfsandwich Complexes Ph3P=N–Nb(η5-C5EtMe4)Cl3 and [(η5-C5EtMe4)Cl3Nb–N = PPh2]2C2H2
Authors: Leichtweis Iring , Roesky Herbert W. , Noltemeyer Mathias , Schmidt Hans-Georg 
Published: March 2015

Cp*NbCl4 (1) (Cp* = η5-C5Me5) and (η5-C5EtMe4)NbCl4 (2) are synthesized in moderate yields by reaction of NbCl5 with the corresponding silanes.
Compound 1 reacts with Me2S(O)=NSiMe3 (3) or Ph3P=NSiMe3 (4) to form the complexes Me2S(O)=N–NbCp*Cl3 (5) and Ph3P=N–NbCp*Cl3 (6). Treatment of 2 with 4 or (Me3SiN=PPh2)2C2H2 (7) yields Ph3P=N–Nb(η5-C5EtMe4)Cl3 (8) and [(η5-C5EtMe4)Cl3Nb-N=PPh2]2C2H2 (9). Products 8 and 9 were characterized by X-ray structure analysis.
Synthese und Strukturuntersuchungen von Iodocupraten(I) / Synthesis and Structure Investigations of Iodocuprates(I)
Authors: Adam Dirk , Herrschaft Bernhard , Hartl Hans 
Published: March 2015

Reactions of CuI with N-methylpyrazinium iodide, (pyr)I, N-methyl-4,4′-bipyridinium iodide, (bp4)I and N-methyl-2,2′-bipyridinium iodide, (bp2)I, in organic solvents led to three novel types of copper(I) complexes of stoichiometries (pyr)Cu2I3, (bp4)Cu3I4 and (bp2)Cu2I3. In all of them the cations are n-σ-bonded to copper(I) through donation of their unshared electron pairs. (pyr)Cu2I3 crystallizes with an ionic structure (trigonal, R 3 c, hexagonal axes a = 3053(2), c = 671.9(3) pm, Z = 18). Polymeric cations ∞
1[((pyr)CuI3/3)3]3+ and anions ∞
1[CuI4/2]-form parallel rod packings. The structure motif of the cations can be described as a columnar part of the β-CuI structure in which the copper and iodine atoms are also arranged to Cu3I3 rings.
The crystal structure of (bp4)Cu3I4 (triclinic, P Ī, a = 938.8(2), b = 980.0(4), c = 1070.1(3) pm, α = 73.56(3), β = 75.79(2), γ = 89.50(3)°, Ζ = 2) is built up by uncharged chains ∞
1[(CuI4/3)(CuI3/3I1/2)((bp4)CuI2/3I1/2)]. The trinuclear units (bp4)Cu3I4 are connected via common iodide edges. The copper halide connection motif of the polymeric compound has some features in common with the “stair” and “cube” structures of adducts of CuI with unidentate, neutral P-, As- or N-bases.
The compound (bp 2)Cu2I3 (monoclinic, P 21/n, a = 1054.0(2), b = 1034.8(3), c = 1512.6(3) pm, β = 108.10(2)°, Ζ = 2) has a structure, in which two edge-sharing (CuI4/2)-tetrahedra and two approximately planar (CuI2/2(bp 2))-units form tetranuclear molecules (bp 2)2Cu4I6. These are linked to chains with a “stair” motif by intermolecular Cu ··· I contacts.
[Al2P4]6-, [Al2As4]6-, [Ga2P4]6- und [Ga2As4]6-, Zintl-Anionen mit 1,3-Dimethylencyclobutan-Struktur / [Al2P4]6-, [Al2As4]6-, [Ga2P4]6- and [Ga2As4]6-, Zintl Anions with 1.3-Dimethylene-cyclobutane Structure
Authors: Somer M. , Thiery D. , Peters K. , Walz L. , Hartweg M. , Popp T. , von Schnering H. G. 
Published: March 2015

The compounds Cs6M2X4 (M = Al, Ga; X = P, As) were synthesized from stoichiometric mixtures of Cs, M and Cs4X6 in sealed Nb ampoules at 950 K. They are isotypic and crystallize in the monoclinic space group P21/c (No. 14) with Z = 4 formula units per unit cell. The anion partial structure is characterized by isolated [M2X4]6- units with relatively short distances for the terminal d(M–X) bonds corresponding to a Pauling Bond Order PBO = 1.5. The distances d(M–X) of the four-membered M2X2 rings correspond to single bonds.
The FIR spectra have been interpreted on the basis of the [M2X4]6- units with 2/m 2/m 2/m-D2h, symmetry by considering a factor group splitting. The assignment of the observed frequencies is supported by a normal coordinate analysis.
Fluoro-, Chloro- und Bromo-Wolfram(VI)-Alkinkomplexe. Die Kristallstrukturen von [K(18-Krone-6)][WF5(Ph – C≡C – H)] · CH3CN und [WCl4(Ph – C ≡ C – Se – n – C4H9)(CH3CN)] / Fluoro-, Chloro-, and Bromo-Tungsten(VI) Alkyne Complexes. The Crystal Structures of [K(18-Crown-6)][WF5(Ph — C ≡ C — H)] · CH3CN and [WCl4(Ph — C ≡ C — Se — n — C4H9)(CH3CN)]
Authors: Neumann Petra , Dehnicke Kurt , Fenske Dieter , Baum Gerhard 
Published: March 2015

Several tungsten alkyne complexes of the type [WCl4(R – C ≡ C – H)]2 and [WCl4(R – C ≡ C — R′)]2 have been prepared by reactions of WCl6 with the alkynes in the presence of C2Cl4. Treating with BrSiMe3 leads to corresponding bromo complexes, whereas reactions of NaF and KF, respectively, in acetonitrile solution in the presence of crown ethers yield the fluoro complexes [Na(15-crown-5)][WF5(R – C ≡ C – R′)] and [K(18-crown-6)][WF5(R – C ≡ C – R ′)], respectively. All complexes were characterized by IR and 13C NMR spectroscopy. The crystal structures of [K(18-crown-6)][WF5(Ph – C ≡ C – H)] · CH3CN and [WCl4(Ph – C ≡ C – Se – n – C4H9)(CH3CN)] have been determined by X-ray methods.
[K(18-crown-6)][WF5(Ph – C ≡ C – H] · CH3CN: Space group P21 Z = 2, 8555 observed unique reflections, R = 0.034. Lattice dimensions at -70 °C: a = 1199.4(3), b = 893.4(2), c = 1351.8(3) pm, β = 109.73(3)°. The compound forms ion pairs via three K – F contacts with bond lengths of 262.0, 282.7, and 293.3 pm; the potassium ion is thus nine-fold coordinated by the six oxygen atoms of the crown ether molecule and by three fluoride ligands. The alkyne ligand is bonded side on to the tungsten atom of the [WF5(Ph – Cs ≡ C – H)]- unit with WC bond lengths of 202.4 and 202.6 pm, respectively.
[WCl4(Ph – C ≡ C – Se – n – C4H9)(CH3CN)]: Space group P21/a, Z = 4,4595 observed unique reflections, R = 0.058. Lattice dimensions at -70 °C: a = 1030.3(5), b = 1596.3(9), c = 1170.9(7) pm, β = 104.28(3)°. The compound has a molecular structure, in which the tungsten atom is seven-fold coordinated by four chloride ligands, by the two alkyne carbon atoms (WC bond lengths 200 and 203 pm), and in trans position to the latter by the nitrogen atom of the acetonitrile molecule with a W – N bond length of 226 pm.
Übergangsmetallkomplexe mit Schwefelliganden, LXXVI Redox- und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (NMe4)2[Ni(′S2′)2] und [Ni(′S4 – C3′)(PMe3)] / Transition Metal Complexes with Sulfur Ligands, LXXVI Redox and Addition Reactions of Nickel Complexes with Multidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (NMe4)2[Ni(′S2′)2] and [Ni(′S4–C3′)(PMe3)]
Authors: Sellmann Dieter , Fünfgelder Stefan , Knoch Falk , Moll Matthias 
Published: March 2015

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).
Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.
The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.