bluuebunny/crossref_metadata_2025_split huggingface dataset:
Neutrale und kationische Eisen-Schwefel-Komplexe und -Cluster Synthese und Kristallstrukturen von [Fe(SR)2L2] · PhMe und [Fe4S4(SR)2L2] sowie zur Bildung von [Fe(SR)L3]+, [FeL4]2+, [Fe4S4(SR)L3]+ und [Fe4S4L4]2+ (R = 2,4,6-i-Pr3C6H2; L = SC(NMe2)2) / Neutral and Cationic Iron-Sulfur Complexes and Clusters Syntheses and Crystal Structures of [Fe(SR),L2] · PhMe and [Fe4S4(SR)2L2], and on the Formation of [Fe(SR)L3]+, [FeL4]2+, [Fe4S4(SR)L3]+ and [Fe4S4L4]2+ (R = 2,4,6-i-Pr3C6H2; L = SC(NMe2)2)
Authors: Bierbach Ulrich , Saak Wolfgang , Haase Detlev , Pohl Siegfried 
Published: March 2015

The reaction of [FeI2L2] (1; L = SC(NMe2)2) with KSR (R = 2,4,6-i-Pr3C6H,) yields [Fe(SR)2L2] · PhMe (2).
Oxidation of the thiolate ligands of 2 with ((Me2N)2CSSC(NMe2)2)2+ affords the cationic complexes [Fe(SR)L3]+ and [FeL4]2+, which were isolated as tetraphenylborate salts.
A mixed ligand neutral iron sulfur cluster [Fe4S4(SR)2L2] (3) has been synthesized by the reaction of 2 with elemental sulfur. 3 is a precursor for cationic clusters which are obtained via the above-mentioned oxidation. The structures of 2 and 3 were determined from single crystal X-ray diffraction data.
2 crystallizes in the monoclinic space group C2/c with a = 1807.8(1), b = 1000.6(1), c = 2946.0(2) pm, β = 101.16(1), V = 5227.6 × 106 pm3, Ζ = 4, R = 0.067. The complex exhibits C2-symmetry and a distorted tetrahedral coordination of Fe(II) (S–Fe–S angles between 101.7 and 125.7). The Fe–Sthiourea and Fe–Sthiolate bond lengths were found to be 240.3(2) and 231.5(1) pm, respectively.
3: triclinic, P1, a= 1020.2(2), b = 1035.3(2), c = 1402.1(2) pm, α = 73.50(1), β = 70.47(1), γ=84.38(1),V= 1338.2 × 106pm3,Z= 1, R = 0.039.
3 shows a slightly compressed Fe4S4 core structure. The Fe– Fe distances range from 269.1 to 278.1 pm. The shortest and longest distances are observed between those Fe atoms which have two thiourea and two thiolate ligands, respectively.
Synthese und Kristallstruktur von Bis(o-aminobenzonitril)-diquecksilber(I)-dinitrat / Synthesis and Crystal Structure of Bis(o-aminobenzonitrile)dimercury(I)-dinitrate
Authors: Brodersen Klaus , Hofmann Jürgen 
Published: March 2015

[Hg2(o-NH2C6H4CN)2](NO3)2 is formed by the reaction of o-aminobenzonitrile with dimercury(I)-dinitrate in methanol. It crystallizes in the monoclinic space group P 2/c with a = 8.6819(5)Å, b = 5.3696(6)Å, c = 19.7645(8)Å, β = 95.138(12)° and Ζ = 2. The crystal structure has been determined by single crystal X-ray diffraction with applied gaussian absorption correction and refined to an Rw-value of 0.027.
The Hg2
2+-ion is coordinated to both amino nitrogen atoms. Strong hydrogen bonds and bridging nitrate ions lead to chain structure.
Synthese und Kristallstrukturen von Tris(glykolato)molybdän(VI) und Tris(pinakolato)molybdän(VI) / Syntheses and Crystal Structures of Tris(glycolato)molybdenum(VI) and Tris(pinacolato)molybdenum(VI)
Authors: Buth Silke , Wocadlo Sigrid , Neumüller Bernhard , Weller Frank , Dehnicke Kurt 
Published: March 2015

PPh4[MoN(OPh)4] has been prepared by reaction of PPh4[MoNCl4] with sodium phenolate, as an orange-red crystal powder. The reactions of glycole and pinacole, respectively, with MoN(O-t-Bu)3 and MoNCl3, the latter in the presence of a base, lead to the tris-chelate complexes Mo(OC2H4O)3 and Mo(OC2Me4O)3, respectively. The complexes were characterized by 1H and 13C NMR spectroscopy, the chelate complexes in addition by X-ray structure analysis.
[Mo(OC2H4O)3]: Space group P21/c, Z = 4, 2177 observed unique reflections, R = 0.047. Lattice dimensions at –40 °C: a = 1168.3(2), b = 716.0(1), c = 1206.1(2) pm, β = 92.84(1)°. [Mo(OC,Me4O)3] • 2CH2Cl2: Space group P bcn, Z = 4, 1860 observed unique reflections, R = 0.049. Lattice dimensions at –80°C: a = 1772.3(1), b = 1023.8(1), c = 1600.0(2) pm.
Both complexes form monomeric molecules, in which the molybdenum atoms are surrounded in a distorted octahedral fashion by the six oxygen atoms of the chelates.
Nitridocuprate(I): Quaternäre Phasen in den Systemen Li—Ca/Sr—Cu—N / Nitridocuprates(I): Quaternary Phases in the Systems Li—Ca/Sr—Cu—N
Authors: Jäger Jürgen , Kniep Rüdiger 
Published: March 2015

The crystal structures of the intermediate phases in the quaternary systems Li–Ca/Sr–Cu–N are characterized by structural units containing substitutional positions (Li1-xCux) in two-fold and linear coordination by nitrogen. The bond-lengths (Li1-xCu1-x)–N are shortened with increasing Cu-content.
SrLi2[(Li1-xCux)N]2: Isotype of Li4SrN2; 0 ≦ x ≦ 0.39 (I 41/amd; Z = 4; x = 0.39: a = 377.0(1) pm, c = 2736.8(6) pm). (Li0.61Cu0.39)–N: 188.5(3) pm.
Sr[(Li1-xCux)N]: Isotype of Ba[NiN]; 0.33 ≦ x ≦ 0.52 (Pnma; Z = 12; x = 0.52: a = 900.1(3) pm, b = 1315.1(5) pm, c = 546.4(1) pm). (Li0.42Cu0.58)–N: 189.0(13) pm.
Ca2{(Li1-xCux)(a)[(Li1-xCux)(b)N2]}: Isotype of Sr2{Li[CoN2]}; 0.03 ≦ x(a) ≦ 0.27, 0.72 ≦ x(b) ≦ 0.80 (P42/mnm; Z = 2; x(a) = 0.27/x(b) = 0.80: a = 529.3(1) pm, c = 663.1(2) pm). (Li0.73Cu0.27)(a)—N: 188.0(7) pm; (Li0.20Cu0.80)(b)–N: 186.2(7) pm.
Based on the experimental results the bond-length CuI–N of two-fold (linear) coordinated Cu(I) in nitrido-compounds is estimated to be 184.5(5) pm.
Die Kristallstrukturen von (PPh4)2[TiCl3(NSiMe3)]2 • CH3CN und (PPh4)2[TiCl4(OSPCl2)]2 / The Crystal Structures of (PPh4)2[TiCl3(NSiMe3)]2 · CH3CN and (PPh4)2[TiCl4(OSPCl2)]2
Authors: Wollert René , Wocadlo Sigrid , Dehnicke Kurt , Goesmann Helmut , Fenske Dieter 
Published: March 2015

(PPh4)2[TiCl3(NSiMe3)]2 · CH3CN has been prepared from [TiCl2NSiMe3)]∞ with PPh4Cl in acetonitrile solution as yellow crystals. The compound crystallizes in the triclinic space group P T with one formula unit per unit cell, 3447 observed unique reflections, R = 0.053. Lattice dimensions at 200 K: a = 1030(1), b = 1253(1), c = 1374(1) pm, α = 77.46(8)°, β = 73.93(8)°, γ = 69.99(9)°. The structure consists of PPh4
+ ions and centrosymmetric dimeric anions [TiCl3(NSiMe3)]2
2-, in which pentacoordinate titanium atoms are associated via the nitrogen atoms of the silylimido groups.
(PPh4)2[TiCl4(OSPCl2)]2 has been prepared by the reaction of PPh [OSPCl2] with titanium tetrachloride in CH2C12 solution as orange crystals. (Space group P1̄, Ζ = 1, 3242 observed unique reflections, R = 0.033). Lattice dimensions at 193 K: a = 1114.8(2), b = 1190.6(2), c = 1218.7(2) pm, α = 72.18(1)°, β = 85.45(1)°, γ = 69.19(1)°. The structure consists of PPh4
+ ions and centrosymmetric dimeric anions [TiCl4(OSPCl2)]2
2-, in which hexacoordinate titanium atoms are associated via two chlorine atoms. The OSPCl2- group is coordinated via the oxygen atom.
Crystal and Molecular Structure and Properties of Tetrasodium<br />[Bis { (µ-isothiocyanato-N,S)(N-salicylidene-β-alaninato) } dicuprate(II)] Dithiocyanate Tetrahydrate
Authors: Kettmann V. , Krätsmár-Šmogrovič J. , Švajlenová O. , Žemlička M. 
Published: March 2015

The binuclear antiferromagnetically superexchange-coupled aquabis(N-salicylidene-β-alaninato)dicopper(II) monohydrate reacts with NaSCN to yield a complex cuprate(II) of stoichiometry Na2Cu(sal-β-ala)(NCS)2 · 2 H2O. The compound has a magnetic moment μ/eff = 1.85. μΒ (Τ = 295 K), and an axial EPR spectrum with g11 > g⊥.
The crystal and molecular structure of the title compound has been determined and refined to R = 0.055 (Rw = 0.062) for 1535 observed reflections, [I &gt; 2σ(I)]. The crystals are triclinic, space group P1̅, with cell dimensions: a = 6.989(3), b = 10.445(5), c = 12.692(6)Å; α = 84.88(5), β = 70.13(4), and γ = 86.72(6)°, V = 869 Å3; Z = 2. The coordination environment of the Cu(II) atom is axially distorted square pyramidal (4 + 1). The basal plane of the pyramid is formed by the 01, Ν 1, and O 2 donor atoms of the tridentate sal-β-ala(2—) Schiff base ligand and by the N 2 atom of the additional NCS(1—) ligand. The apex of the pyramid is occupied by the weakly contacting S l′ atom of the bridging —NCS— ligand, Cu—S 1′ = 2.933(2) Å, thereby giving rise to [Cu2(sal-β-ala)2(μ-NCS)2]2- centrosymmetric binuclear complex anion. The remaining components of the crystal structure are SCN- (uncoordinated to Cu2+), Na+ ions, and H2O molecules.
Synthese und Kristallstruktur von Bromotriphenylphosphoniumtribromid, [(C6H5)3PBr]Br3 / Synthesis and Crystal Structure of Bromotriphenylphosphonium Tribromide, [(C6H5)3PBr]Br3
Authors: Vogt H. , Trojanov S. I. , Rybakov V. B. 
Published: March 2015

Bromotriphenylphosphonium tribromide, [(C6H5)3PBr]Br3, has been prepared by the reaction of triphenylphosphine with bromine in dichloromethane. Light-brown crystals are obtained by recrystallization from the same solvent.
The crystal and molecular structure of the title compound has been determined. The crystals are monoclinic, space group P21/c, Z = 8; a = 1917.1(8), b = 1182.2(9), c = 1823.5(4) pm, β = 108.34(2)°. R = 0.056 (Rw = 0.063) for 1813 reflections with I ≥ 3σ(I). In the solid state the title compound exists as discrete monomeric (C6H5)3PBr+ and Br3⁻ ions with two crystallographically independent ions of each sort. The cations have a slightly irregular tetrahedral geometry around the P atom. The tribromide anions are nearly symmetrical and slightly bent.
Biomimetische Photosysteme zur sakrifiziellen Wasserreduktion / Novel Biomimetic Systems for Visible Light Induced Water Reduction
Authors: Boßmann Stefan , Dürr Heinz , Mayer Eduard 
Published: March 2015

Novel microheterogeneous systems for the direct photoreduction of water using visible light in analogy to the photochemical reaction center of Rhodopseudomonas viridis are described in detail. These physical model systems for photosynthesis feature the recently synthesized bisheteroleptic metal complexes [Ru(bpy)2(PP)]Cl2, [Ru(bpy)2(PPB)]Cl2, [Ru(bpy)2(PPB-pCl)]Cl2 and [Ru(bpy)3]Cl2, adsorbed on a negatively charged SiO2—TiO2-colloid, the zwitterionic electron relay PVS and a long-term stable and highly efficient TiO2—Pt-“antenna” catalyst as well as TEOA as sacrificial electron donor.
Evidence for the directed absorption of the sensitizers on the SiO2—TiO2-colloid is taken from UV-VIS-measurements, steady-state luminescence-spectroscopy and the quantum yields for PVS-reduction.
The hydrogen production in the presence of the SiO2—TiO2-colloid is clearly enhanced and proofs the validity of the underlying concept of physical model systems for photosynthesis.
Koordinationschemie perhalogenierter Cyclopentadiene und Alkine, XI [1].<br />Darstellung einiger Cymantrenyl-mono- und bis-thioether mit einer weiteren funktionellen Gruppe am Cyclopentadienylring. Molekülstruktur von [C5Cl2(SMe)2(PPh2)]Mn(CO)3 / Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, XI [1]<br />Synthesis of Some Cymantrene Mono- and Bis-Thioethers with One Additional Functional Group on the Cyclopentadienyl Ring. Molecular Structure of [C5Cl2(SMe)2(PPh2)]Mn(CO)3
Authors: Sünkel Karlheinz , Blum Adrian , Wagner Barbara 
Published: March 2015

Chiral Cyclopentadienyl Complexes, Crystal Structure
The reaction of [C5Cl4(SMe)]Mn(CO)3 (la) with n-butyllithium and the electrophiles SiMe3Cl, CO2, or PPh2Cl regiospecifically yields the chiral 1,3-disubstituted functional cymantrene thioethers [C5Cl3(SMe)R]Mn(CO)3 (R = SiMe3 (2), COOLi (3a), PPh2 (4)). 3 a can be protonated to give the corresponding carboxylic acid (3b), which in turn can be transformed to the acid chloride [C5Cl3(SMe)(COCl)]Mn(CO)3 (3c). 3c reacts with NaN3 to yield after work-up the urea derivative OC[[NH—C5Cl3(SMe)]Mn(CO)3]2 (3d). Using the cymantrene bisthioethers [C5Cl3(SR)2]Mn(CO)3 (R = Me, 5a, Ph, 5b) as starting materials, the carboxyl derivatives [C5Cl2(SMe)2(COR)]Mn(CO)3 (R = OLi, 6a, OH, 6b, Cl, 6c) and the potential organometallic S,P-chelate ligands [C5Cl2(SR)2(PPh2)]Mn(CO)3 (R = Me, 7a, Ph, 7b) can be obtained. The crystal structure determination of 7a (C22H16O3PS2Cl2Mn, monoclinic, P 21/c, a = 18.714(6) A, b = 9.506(3) A, c = 14.475(3) Α, β = 109.18(2)°, V = 2432.1(12) Α3, Z = 4) shows an orientation of the neighbouring PPh2- and SMe groups, that allows chelation of an additional metal fragment.
Fünffach koordinierte Co(III)-Komplexe [Tripod-Cobalt-(ortho(X)(Y)C6H4)]+ mit ortho-phenylenverbrückten Chelatliganden [(XH)(YH)C6H4] (XH, YH = NH2, OH, SH) / Five-Coordinate Co(III) Complexes [Tripod-Cobalt-(ortho-(X)(Y)C6H4)]+ Containing ortho-Phenylene-Bridged Chelate Ligands [(XH)(YH)C6H4] (XH, YH = NH2, OH, SH)
Authors: Vogel Sabine , Huttner Gottfried , Zsolnai Laszlo 
Published: March 2015

The ortho-phenylene compounds ortho-[(XH)(YH)C6H4] (XH, YH = NH2, SH, OH) react with Co(BF4)2•6H2O and Tripod (CH3C(CH2PPh2)3) to give the five-coordinate Co(III) complexes [Tripod-Cobalt-(ortho-(X)(Y)C6H4)]+ (X, Y = NH, O, S), 1-6.
The structures of 1—6 have been characterized by X-ray analyses of appropriate salts. The compounds have further been characterized by IR, NMR, UV-VIS and cyclovoltammetric measurements.
As a compound analogous to 1—6, but containing the saturated chelate ligand [(S)C2H4(S)]2- instead of the conjugated ortho-phenylene type ligands of 1-6, [Tripod-Cobalt-((S)C2H4(S))]+, 7, has been prepared and fully characterized. It is inferred that the coordination geometries of 1-7 do not strongly depend on conjugative interaction within the chelating ligands.
Notizen: The Crystal Structure of β-CsReO4, the Room-Temperature Modification of Cesium Perrhenate
Authors: Rögner Peter , Range Klaus-Jürgen 
Published: March 2015

The crystal structure of β-CsReO4, the roomtemperature modification of cesium perrhenate, was determined from single-crystal X-ray data as orthorhombic, space group P nma, a = 5.7556(9), b = 5.9964(8), c = 14.310(2) Å and Z = 4.
The structure was refined to R = 0.027, Rw = 0.023 for 779 absorption-corrected reflections. It represents an orthorhombic distortion of the tetragonal high-temperature phase α-CsReO4. The structure of β-CsReO4 comprises isolated ReO4 tetrahedra, linked together by Cs ions. The average Re-O distance was found to be 1.714(4) Å.
Notizen: The Crystal Structure of Cesium Fluorotrioxosulfate(VI), CsSO3F
Authors: Rögner Peter , Range Klaus-Jürgen 
Published: March 2015

The crystal structure of CsSO3F was determined from single-crystal X-ray data as tetragonal, space group I4,/amd, with a = 5.6317(2), c = 14.1991(9) Å and Z = 4. The structure was refined to R = 0.028,Rw = 0.028 for 403 unique reflections.
In contrast to the earlier literature CsSO3F is not isomorphous with scheelite but with α-CsReO4. The structure contains isolated SO3F tetrahedra which are linked together by twelvefold coordinated Cs ions. The average S–O,F distance is 1.453(3) Å.
Oxa-azonia-boratacyclopentanes by Insertion of Dimethylaminobis(trifluoromethyl)borane into Epoxides
Authors: Bürger Hans , Hagen Thomas , Pawelke Gottfried 
Published: March 2015

Dimethylaminobis(trifluoromethyl)borane, (CF3)2BNMe2 (A), reacts with epoxides of the general formula

to yield five-membered heterocycles
(CF3)2

, R = Me (1), CH,F (2), CF3 (3), Et (4), Bz (5). With R = Ph a 1:2 mixture of the isomers (CF3)2

O (6a) and (CF3)2

(6b) is obtained. To the contrary,

and A form the borane-dimethylamine adduct (H2C=CMe—CH2-O)(CF3)2B • NHMe2 (7). The compounds have been characterized by elemental analyses, multinuclear NMR, IR and mass spectra.
Zinn(IV)-Verbindungen mit Ferrocenylchalkogenat- und Ferrocenylendichalkogenat-Liganden. Synthese und Multikern-NMR-Spektroskopie / Tin(IV) Compounds Containing Ferrocenyl Chalcogenate and Ferrocenylene Dichalcogenate Ligands. Synthesis and Multinuclear NMR Spectroscopy
Authors: Herberhold Max , Hübner Michaela , Wrackmeyer Bernd 
Published: March 2015

A series of tin(IV) compounds containing ferrocenyl chalcogenate (FcE) and ferrocenylene dichalcogenate (fcE2) ligands (E = S, Se, Te) has been synthesized for a systematic study of the NMR spectra with particular emphasis on 13C, 119Sn, 77Se and 125Te NMR. All compounds are formally derived from tetramethylstannane, SnMe4, by stepwise replacement of methyl by either FcE or fcE2 ligands. Starting from lithioferrocene the products are tetrasubstituted stannanes Me4-nSn(EFc)n (n = 1 and 2, E = S, Se, Te; n = 3 and 4, E = S, Se). Starting from 1,1′dilithioferrocene, the products are 1,1′-disubstituted ferrocenes such as fc(E-SnMe3)2 (E = S, Se, Te), although 1,3-dichalcogena[3]ferrocenophane rings are formed whenever possible to give [3]ferrocenophanes fcE2SnMe2 (E = S, Se, Te) and fc[E-Sn(Me)E2fc]2 (E = S, Se) or tin spiro compounds Sn(E2fc)2 (E = S, Se, Te). Whereas all (8) possible sulfur-containing and all (8) selenium-containing products were accessible, some of the tellurium-rich compounds could not be isolated due to preferred formation of either Fc2Te2 or fcTe3.
All compounds were characterized on the basis of their 1H, 13C, 119Sn and, if possible, 77Se and 125Te solution NMR spectra. In many cases, coupling constants such as 2J(119Sn1H), nJ(119Sn13C) (n = 1,2,3), 1J(119Sn77Se) and 1J(125Τe119Sn), 1J(77Se13C) and 1J(125Te13C) could be determined. The δ119Sn chemical shifts of analogous phenyl and ferrocenyl compounds, Me4-nSn(EPh) and Me4-nSn(EFc)n (n = 0-4, E = S, Se, Te), are discussed, and for a microcrystalline sample of tetrakis(ferrocenylselenolato)stannane, Sn(SeFc)4, the 119Sn and 77Se CP/MAS NMR spectra are reported and compared with the solution spectra.
Hydrogen Bonding in Crystals of an Ammonium Catecholate NH4[C6H4(OH)2][C6H4(OH)O] · 0.5 H2O
Authors: Kumberger Otto , Riede Jürgen , Schmidbaur Hubert 
Published: March 2015

A discrete ammonium catecholate hydrate of the composition
NH4[C6H4(OH)2][C6H4(OH)O] · 0.5 H2O has been isolated and characterized by a single-crystal X-ray structure analysis. The crystals are monoclinic, space group C 2/c (No. 15), Z = 8, a = 24.613(3), b = 8.706(1), c = 11.890(2) Å, β = 110.56(1)°. The crystal lattice features a network of hydrogen bonds, which clearly contribute significantly to the overall stability of the lattice. The water molecule is engaged as a donor and an acceptor in as many as four hydrogen bonds. Surprisingly, the crystalline compound is air-stable, while anhydrous ammonium catecholate, as obtained by dissolving catechol in dry liquid ammonia, is quickly oxidized in air.
Cl NQR Spectra of Some New Iridium Chlorochalcogenide Complexes
Authors: Fokina Z. A. , Pekhnyo V. I. , Volkov S. V. , Lapko V. F. , Bryukhova Y. V. , Kuznetsov S. I. 
Published: March 2015

The 35C1 NQR spectra of the chlorochalcogenide complexes of iridium (SCl3)2 [IrCl6] 1, (TeCl3)2 [IrCl6] 2, (SeCl3) [IrCl6] 3, [IrCl3(SCl2)2]2 4, (SCl3) [IrCl4(SCl2)2] 5 and [IrCl3(SeCl2)2]2 6 have been studied. The spectra were recorded by pulse spectrometry. They consist of two mul tiplets, widely separated in frequency. The high-frequency multiplet belongs to the chlorine atoms bonded to sulfur, selenium and tellurium, respectively, in the ligand. A high-frequency shift is observed, which is typical for the coordination of the molecules ACl2(A=S, Se) and ACl4(A=S, Se, Te). The low frequencies in the multiplets of 4 and 6 are attributed to additional bonds formed between chalcogen atom and chlorine in the coordination environment of iridium.
In the spectral region 18-24 MHz lie the NQR frequencies of 35Cl bonded to iridium. For 2 the frequencies are close to those of [IrCl6]2-, which confirms the Ir oxidation state IV. The unexpectedly high frequencies for IrIII in the case of 4 and 5 are explained by the influence of ACl2 molecules, which are weaker σ-donors than the chloro ligands. This promotes electron density transfer from neighbouring chlorine atoms. The 18 MHz frequency is assigned to the bridge chlorine atoms in dimeric molecule 4. This assignment is confirmed by the positive value of d v/dT = +0,2.
Verbindungen mit SiS2-isosteren Anionen ∞
1[AlX4/2
3-] und ∞
1[InP4/2
3-]: Synthesen, Kristallstrukturen und Schwingungsspektren von Na3[AlX2], K2Na[AlX2] und K3[InP2] (X = P, As) / Compounds with SiS2 Isoelectronic Anions ∞
1[AlX4/2
3-] and ∞
1[InP4/2
3-]: Synthesis, Crystal Structures and Vibrational Spectra of Na3[AlX2], K2Na[AlX2] and K3[InP2] (X = P, As)
Authors: Ohse Lothar , Somer Mehmet , Blase Wolfgang , Cordier Gerhard 
Published: March 2015

The title compounds were prepared from stoichiometric mixtures of the elements or from alkali metals (Na, K), NaX (KX) and MX (M = Al, In; X = P, As) at 1000 K. The crystal structures (Ibam, No. 72) are characterized by infinite chains of edge sharing tetrahedra ∞
1[MX4/2
3-] (M = Al, In; X = P, As) which are isoelectronic to SiS2.
The vibrational spectra can be interpreted with respect to the symmetry P(2/m 2/c) 42/m–D4h of the isolated polymeric chain ∞
1[MX4/2
3-]. The assignment of the observed frequencies is supported by a normal coordinate analysis using the fragment method.
Sulfurization and Selenization of the Halfsandwich Nitrosylmetal Complexes Cp*M(CO)2NO (M = Cr, Mo) and Cp*M(NO)I2 (M = Mo, W)
Authors: Herberhold Max , Jin Guo-Xin , Rheingold Arnold L. 
Published: March 2015

The photo-induced decarbonylation of Cp*Cr(CO)2NO in acetonitrile solution in the presence of excess sulfur leads to the cyclo-pentasulfido complex Cp*Cr(NO)(S5) (1 a), while in the case of limited sulfur supply the binuclear bis(µ-disulfido) complex Cp*2Cr2(NO)2(µ-S2)2 (4a) is formed preferentially. The corresponding reaction with elemental selenium produces Cp*2Cr2(NO)2(µ-Se2)2 (4b), irrespective of the available amount of selenium. Photodecarbonylation of Cp*Mo(CO)2NO gives only the binuclear derivates Cp*2Mo2(NO)2(µ-E2) (E = S (5a), Se (5b)) which are also obtained by treating Cp*Mo(NO)I2 with H2S or H2Se, respectively. Nitrosyl loss predominates if the tungsten complex Cp*W(NO)I2 is reacted with H2S; in an argon atmosphere the products are Cp*W(S)(S2)(I) (7a) and Cp*2W2(S)2(µ-S)2 (8a), while in air some Cp*W(NO)(S5) (3a) and the oxo compounds Cp*W(O)(S2)I (7c), Cp*2W2(O)2(µ-S)2 (8c) and Cp*2W2(S)(O)(µ-S)2 (8d) are formed. The analogous reaction with H2Se leads to Cp*W(NO)(Se5) (3b), Cp*2W2(O)2(µ-Se)2 (9c) and Cp*2W2(Se)(O)(µ-Se)2 (9d), respectively. The binuclear tungsten complexes 8a,c,d and 9c,d contain a central W(µ-E)2W framework (E = S or Se) which is unaffected by air, while terminal sulfido and selenido ligands are quantitatively converted into the corresponding terminal oxo ligands in the presence of air in CH2C12 or THF solution. With the preparation of Cp*2W2(O)2(µ-E)2 (E = S (8c) and Se (9c)), the series of dioxo complexes containing a pair of monochalcogen bridges (E = O, S, Se, Te) has become complete.
The new complexes have been characterized by their IR (v(NO)), 1H and 13C NMR (Cp*) spectra as well as by electron-impact mass spectrometry. According to the X-ray structure analyses, the binuclear compounds Cp*2Cr2(NO)2(µ-S2)2 (4a) and Cp*2Mo2(NO)2(µ-Se2)2 (5b) contain two 14-electron [Cp*M(NO)2] fragments which are connected by a pair of dichalcogen (η1,η2-E2) bridging ligands (M = Cr or Mo, E = S or Se). The central M2E2 four-membered ring is not planar, and the binuclear molecules are chiral.