Darstellung,Charakterisierung und Struktur funktionalisierter Fluorphosphaalkene des Typs R3E–P=C(F)NEt2 (R/E = Me/Si,Me/Ge,CF3/Ge,Me/Sn)

Preparation, Characterization, and Structure of Functionalized Fluorophosphaalkenes of the Type R₃E–P=C(F)NEt₂ (R/E = Me/Si, Me/Ge, CF₃/Ge, Me/Sn) P‐functionalized 1‐diethylamino‐1‐fluoro‐2‐phosphaalkenes of the type R₃E–P=C(F)NEt₂ [R/E = Me/Si ( 2 ), Me/Ge ( 3 ), CF₃/Ge ( 4 ), Me/Sn ( 5 )] are prepared by reaction of HP=C(F)NEt₂ ( 1 , E/Z = 18/82) with R₃EX (X = I, Cl) in the presence of triethylamine as base, exclusively as Z‐Isomers. 2–5 are thermolabile, so that only the more stable representatives 2 and 4 can be isolated in pure form and fully characterized. 3 and 5 decompose already at temperatures above –10 °C, but are clearly identified by ¹⁹F and ³¹P NMR‐measurements. The Z configuration is established on the basis of typical NMR data, an X‐ray diffraction analysis of 4 and ab initio calculations for E and Z configurations of the model compound Me₃Si–P=C(F)NMe₂. The relatively stable derivative 2 is used as an educt for reactions with pivaloyl‐, adamantoyl‐, and benzoylchloride, respectively, which by cleavage of the Si–P bond yield the push/pull phosphaalkenes RC(O)–P=C(F)NEt₂ [R = tBu ( 6 ), Ad ( 7 ), Ph ( 8 )], in which π‐delocalization with the P=C double bond occurs both with the lone pair on nitrogen and with the carbonyl group.     

Ab‐initio‐Berechnung des Tetracarbonatoscandat‐Ions in Na5[Sc(CO3)4] · 2 H2O. Einkristallstrukturbestimmung,Schwingungsspektren und thermischer Abbau

Ab Initio Calculation of the Tetracarbonatoscandate‐Ion in Na₅[Sc(CO₃)₄] · 2 H₂O. Single Crystal Structure Determination, Vibrational Spectra, and Thermal Decomposition Normal modes of the tetracarbonatoscandate‐ion, [Sc(CO₃)₄]^5–, were determined by ab initio calculations and were compared with experimental data of Infrared‐ and Raman‐spectra of the compound Na₅[Sc(CO₃)₄] · 2 H₂O. A necessary redetermination of the structure with single crystal x‐ray diffraction data (tetragonal, P42₁c (Nr. 114), Z = 2, a = 746,37(4) pm, c = 1157,0(2) pm, V_EZ = 644,5(1) 10⁶ pm³) allows the discussion of existing hydrogen bonds. Determination of the thermal behaviour indicates a two‐stage decomposition reaction, but no corresponding intermediate could be isolated.     

Darstellung und Struktur von [Cp2MoHLi(thf)]3 · Toluol

Synthesis and Crystal Structure of [Cp₂MoHLi(thf)]₃ · Toluene [Cp₂MoHLi]₄ reacts in THF/Toluene to the trimeric complex [Cp₂MoHLi(thf)]₃ · Toluene 1 . The structure of 1 was characterized by X-ray single crystal structure analysis. Space group P6₃, Z = 2, a = 1459.5(9) pm, c = 1182.3(8) pm. The central unit is represented by a Mo₃Li₃-hexagon. Each Mo-Atom is surrounded by two Cp-Ligands. One THF-Molecule is coordinated to each Li-atom. The Hydrogen-Ligand could not be located by the single crystal structure analysis.     

Darstellung und Kristallstrukturen von Silber(I)-Gemischtligandkomplexen mit Bibenzimidazol und Triphenylphosphan: [Ag(PPh3)2(bbimH2)](COOCH3) · 2 CH2Cl2 und [{Ag(PPh3)2}2(μ-bbim)] · 4 CH2Cl2

Preparation and Crystal Structures of Silver(I) Mixed Ligand Complexes with Bibenzimidazole and Triphenylphosphane: [Ag(PPh₃)₂(bbimH₂)](COOCH₃) · 2 CH₂Cl₂ and [{Ag(PPh₃)₂}₂(μ-bbim)] · 4 CH₂Cl₂ The title compounds are obtained from silver acetate, 2,2′-bibenzimidazole and PPh₃. They are characterized by their IR, ¹H-NMR, ³¹P-NMR spectra and crystal structure determinations. [Ag(PPh₃)₂(bbimH₂)](COOCH₃) · 2 CH₂Cl₂: Reaction in CH₂Cl₂. Space group C2/c, Z = 4, 3129 observed unique reflections, R = 0.033. Lattice parameters at 203 K: a = 1450.8; b = 1556.2; c = 2316.4 pm; β = 99.69°. The crystal structure is built up by monomeric molecules with distorted tetrahedral coordination of the silver atom (AgP₂N₂) and bibenzimidazole as a bidentate ligand. The acetate ion is linked to the NH-groups of the bibenzimidazole by hydrogen bonds. [{Ag(PPh₃)₂}₂(μ-bbim)] · 4 CH₂Cl₂: Reaction in fused PPh₃ at 180 °C. Space group P 1, Z = 1. 9227 observed unique reflections, R = 0.051. Lattice parameters at 203 K: a = 1276.5; b = 1352.1; c = 1408.1 pm; α = 96.97; β = 115.87; γ = 96.84°. The crystal structure is built up by centrosymmetric molecules with distorted tetrahedral coordination of the silver atoms (AgN₂P₂) and bibenzimidazolate(2–) as tetradentate bridging ligand.     

Einfluß der Ringatome auf die Struktur von Triel‐Pentel‐Heterozyklen – Synthese und Molekülstrukturen von [Me2InAs(SiMe3)2]2 und [Me2InSb(SiMe3)2]3

Influence of the Ring Atoms on the Structure of Triel‐Pentel Heterocycles – Synthesis and X‐Ray Crystal Structures of [Me₂InAs(SiMe₃)₂]₂ and [Me₂InSb(SiMe₃)₂]₃ Triel‐pentel heterocycles [Me₂InE(SiMe₃)₂]_x have been prepared by dehalosilylation reactions from Me₂InCl and E(SiMe₃)₃ (E = As, x = 2; E = Sb, x = 3) and characterised by NMR spectroscopy and by X‐ray crystal structure analyses. In addition the X‐ray crystal structures of [Me₂GaAs(SiMe₃)₂]₂ and [Me₂InP(SiMe₃)₂]₂ are reported. The compounds complete a family of 13 identically substituted heterocycles [Me₂ME(SiMe₃)₂]_x (M = Al, Ga, In; E = N, P, As, Sb, Bi; x = 2, 3), whose structures were investigated depending on the ring atoms M and E. The tendencies that have been observed concerning the ring sizes can be explained by the interplay of the atomic radii of the central atoms and the sterical demand of the ligands. After a formal separation of the M–E bonds in σ bonds and dative bonds the characteristic differences and trends in the endocyclic and exocyclic bond angles of both centres M and E can be interpreted on the basis of a simple Lewis acid/base adduct model.     

AlCl3 · 2NH3 – eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-tetrachloroaluminats – [AlCl2(NH3)4]+[AlCl4]−

ACl₃ · 2NH₃ – a Compound with the Crystal Structure of a Tetraammine Dichloroaluminiumtetrachloroaluminate – [AlCl₂(NH₃)₄]⁺[AlCl₄]^? Ammoniates of aluminiumchloride AlCl₃ · xNH₃ are in discussion as starting materials for the synthesis of aluminiumnitride. Therefore the reactions of melts of monoamminealuminiumchloride with ammonia were investigated. They react at 150°C within 10 min with one mole of ammonia to the diammoniate, [AlCl₂(NH₃)₄]⁺[AlCl₄]^?. The pure compound can be obtained by sublimation at 200°C in vacuumline apparatus. X-ray structure determination on [AlCl₂(NH₃)₄]⁺[AlCl₄]^? was carried out: see “Inhaltsübersicht”.     

AlCl3 · 3NH3 — eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-diammintetrachloroaluminats: [AlCl2(NH3)4]+[AlCl4(NH3)2]−

AlCl₃ · 3NH₃ — a Compound with the Crystal Structure of a Tetraammine Dichloro Aluminium-Diammine Tetrachloro Aluminate: [AlCl₂(NH₃)₄]⁺[AlCl₄(NH₃)₂]^? . AlCl₃ · 3 NH₃ ? [AlCl₂(NH₃)₄]⁺ [AlCl₄(NH₃)₂]^? forms during the reaction of two mole NH₃ with AlCl₃(NH₃) at T ≥ 200°C. Repeated heating and cooling within 48 h between 200°C and 250°C gives a homogeneous product with total uptake of the necessary amount of NH₃. Slow sublimation in a vacuum line apparatus at 200°C gives crystals of the triammoniate sufficient for a X-ray structure determination: The compound contains elongated [AlCl₂(NH₃)₄]⁺ octahedra and compressed [AlCl₄(NH₃)₂]^? octahedra. Besides ionic bonding hydrogen bridge bonds with 3.369 Å ? d(N—H … Cl) ? 3.589 Å stabilize the atomic arrangement.     

Synthese und Einkristallstrukturanalyse von Bis(benzyltrimethylammonium)fullerid-Ammoniakat; (BzlNMe3)2C60 · 3 NH3

Synthesis and Single Crystal Structure Analysis of Bis(benzyltrimethylammonium)fulleride Ammonia 1/3, (BzlNMe₃)₂C₆₀ · 3 NH₃ The title compound has been prepared from K₂C₆₀ by ion exchange of potassium for benzyltrimethylammonium cations in liquid ammonia. X-ray single crystal structure analysis reveals highly ordered fulleride ions forming a layer-like arrangement with short inter-fullerene distances. The anionic fulleride layers are separated by layers of benzyltrimethylammonium cations and ammonia.     

Synthese und Struktur gemischt‐substituierter Dialane Al2X2{Si(SiMe3)3}2 · 2 THF (X = Cl,Br)

Synthesis and Structure of two Mixed Substituted Dialanes Al₂X₂{Si(SiMe₃)₃}₂ · 2 THF (X = Cl, Br) The syntheses of tris(trimethylsilyl)silyl (hypersilyl) and halide substituted dialanes Al₂X₂{Si(SiMe₃)₃}₂ · 2 THF (X = Cl, Br) are presented. The results of the X‐ray diffraction experiments are presented and discussed in comparison to the Al^III compounds AlBr₂Si(SiMe₃)₃ · THF and AlBr₃ · OPh₂.     

Synthesis and Crystal Structures of the Novel Tetrameric Nitrido Complexes [{cyclo-ReN}4(S2CNEt2)6(MeOH)2(PPh3)2][BPh4]2 · CH2Cl2 · 2 H2O and [{cyclo-ReN}4(S2CNEt2)4Cl4(PMe2Ph)4] · 2 acetone

Novel tetrameric rhenium(V) complexes have been prepared from [ReNCl₂(PPh₃)₂] and [ReN(PMe₂Ph)(S₂CNEt)₂], respectively. [ReNCl₂(PPh₃)₂] reacts with 1.5 equivalents of KS₂CNEt₂ in methanol to yield the unusual dark red species [{cyclo-ReN}₄(S₂CNEt₂)₆(MeOH)₂(PPh₃)₂][BPh₄]₂ · CH₂Cl₂ · 2 H₂O ( 1 ). The crystal structure of the tetramer (triclinic, space group P1, a = 13.842(2), b = 15.213(2), c = 16.796(3) Å, α = 67.88(1), β = 70.90(1), γ = 88.05(1)°, U = 3080.2(8) ų, Z = 1) shows four rhenium atoms in a square configuration which are bridged via linear asymmetric Re≡N–Re groups with bond lengths of about 169 and 203 pm. The molecule contains a centre of symmetry with two distinct octahedral rhenium environments. The first rhenium environment contains two bidentate dithiocarbamate ligands which complete the octahedral geometry and the second contains a bidentate dithiocarbamate ligand, coordinated methanol and has retained a single phosphine coligand. A symmetric compound containing the {cyclo-ReN}₄ core is obtained from the reaction of [ReN(PMe₂Ph)(S₂CNEt₂)₂] with Al₂Cl₆ in acetone. [{cyclo-ReN}₄(S₂CNEt₂)₄Cl₄(PMe₂Ph)₄] · 2 acetone ( 2 ) forms red crystals (monoclinic, space group C2/c, a = 21.432(6), b = 13.700(3), c = 28.060(9) Å, β = 102.37(1)°, U = 8048(4) Å3, Z = 4) with each rhenium atom coordinated by a bidentate dithiocarbamato, a phosphine and a chloro ligand. The non-planar 8-membered {ReN}₄ ring contains asymmetric Re≡N–Re bridges (mean values: 1.69 Å and 2.029 Å, respectively). In contrast, reaction of [ReNCl(S₂CNEt₂)(PMe₂Ph)₂] with one equivalent of K[S₂CN(Me)CH₂CH₂NMe₃]I gave the mixed dithiocarbamato-cation [ReN(S₂CNEt₂)(S₂CN(Me)CH₂CH₂NMe₃)(PMe₂Ph)]⁺ ( 3 ) which was isolated as a tetraphenylborate salt.     

Synthese,Kristallstrukturen und thermisches Verhalten von Er2(SO4)3 · 8 H2O und Er2(SO4)3 · 4 H2O

Syntheses, Crystal Structures, and Thermal Behavior of Er₂(SO₄)₃ · 8 H₂O and Er₂(SO₄)₃ · 4 H₂O Evaporation of aqueous solutions of Er₂(SO₄)₃ yields light pink single crystals of Er₂(SO₄)₃ · 8 H₂O. X-ray single crystal investigations show that the compound crystallizes monoclinically (C2/c, Z = 8, a = 1346.1(3), b = 667.21(1), c = 1816.2(6) pm, β = 101.90(3)°, R_all = 0.0169) with eightfold coordination of Er³⁺, according to Er(SO₄)₄(H₂O)₄. DSC- and temperature dependent X-ray powder investigations show that the decomposition of the hydrate follows a two step mechanism, firstly yielding Er₂(SO₄)₃ · 3 H₂O and finally Er₂(SO₄)₃. Attempts to synthesize Er₂(SO₄)₃ · 3 H₂O led to another hydrate, Er₂(SO₄)₃ · 4 H₂O. There are two crystallographically different Er³⁺ ions in the triclinic structure (P 1, Z = 2, a = 663.5(2), b = 905.5(2), c = 1046.5(2) pm, α = 93.59(3)°, β = 107.18(2)°, γ = 99.12(3)°, R_all = 0.0248). Er(1)³⁺ is coordinated by five SO₄^2– groups and three H₂O molecules, Er(2)³⁺ is surrounded by six SO₄^2– groups and one H₂O molecule. The thermal decomposition of the tetrahydrate yields Er₂(SO₄)₃ in a one step process. In both cases the dehydration produces the anhydrous sulfate in a modification different from the one known so far.     

Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO)4L (L = CO,CS, N2, NO+, CN–, NC–, η2‐C2H4, η2‐C2H2, CCH2, CH2, CF2, NH3, NF3, PH3, PF3, η2‐H2)

Equilibrium geometries, bond dissociation energies and relative energies of axial and equatorial iron tetracarbonyl complexes of the general type Fe(CO)₄L (L = CO, CS, N2, NO⁺, CN^–, NC^–, η²‐C₂H₄, η²‐C₂H₂, CCH₂, CH₂, CF₂, NH₃, NF₃, PH₃, PF₃, η²‐H₂) are calculated in order to investigate whether or not the ligand site preference of these ligands correlates with the ratio of their σ‐donor/π‐acceptor capabilities. Using density functional theory and effective‐core potentials with a valence basis set of DZP quality for iron and a 6‐31G(d) all‐electron basis set for the other elements gives theoretically predicted structural parameters that are in very good agreement with previous results and available experimental data. Improved estimates for the (CO)₄Fe–L bond dissociation energies (D₀) are obtained using the CCSD(T)/II//B3LYP/II combination of theoretical methods. The strongest Fe–L bonds are found for complexes involving NO⁺, CN^–, CH₂ and CCH₂ with bond dissociation energies of 105.1, 96.5, 87.4 and 83.8 kcal mol^–1, respectively. These values decrease to 78.6, 64.3 and 64.2 kcal mol^–1, respectively, for NC^–, CF₂ and CS. The Fe(CO)₄L complexes with L = CO, η²‐C₂H₄, η²‐C₂H₂, NH₃, PH₃ and PF₃ have even smaller bond dissociation energies ranging from 45.2 to 37.3 kcal mol^–1. Finally, the smallest bond dissociation energies of 23.5, 22.9 and 18.5 kcal mol^–1, respectively are found for the ligands NF₃, N₂ and η²‐H₂. A detailed examination of the (CO)₄Fe–L bond in terms of a semi‐quantitative Dewar‐Chatt‐Duncanson (DCD) model is presented on the basis of the CDA and NBO approach. The comparison of the relative energies between axial and equatorial isomers of the various Fe(CO)₄L complexes with the σ‐donor/π‐acceptor ratio of their respective ligands L thus does not generally support the classical picture of π‐accepting ligands preferring equatorial coordination sites and σ‐donors tending to coordinate in axial positions. In particular, this is shown by iron tetracarbonyl complexes with L = η²‐C₂H₂, η²‐C₂H₄, η²‐H₂. Although these ligands are predicted by the CDA to be stronger σ‐donors than π‐acceptors, the equatorial isomers of these complexes are more stable than their axial pendants.     

Carbonat‐Hydrate der schweren Alkalimetalle: Darstellung und Struktur von Rb2CO3 · 1,5 H2O und Cs2CO3 · 3 H2O

Carbonate Hydrates of the Heavy Alkali Metals: Preparation and Structure of Rb₂CO₃ · 1.5 H₂O und Cs₂CO₃ · 3 H₂O Rb₂CO₃ · 1.5 H₂O and Cs₂CO₃ · 3 H₂O were prepared from aqueous solution and by means of the reaction of dialkylcarbonates with RbOH and CsOH resp. in hydrous alcoholes. Based on four‐circle diffractometer data, the crystal structures were determined (Rb₂CO₃ · 1.5 H₂O: C2/c (no. 15), Z = 8, a = 1237.7(2) pm, b = 1385.94(7) pm, c = 747.7(4) pm, β = 120.133(8)°, V_EZ = 1109.3(6) · 10⁶ pm³; Cs₂CO₃ · 3 H₂O: P2/c (no. 13), Z = 2, a = 654.5(2) pm, b = 679.06(6) pm, c = 886.4(2) pm, β = 90.708(14)°, V_EZ = 393.9(2) · 10⁶ pm³). Rb₂CO₃ · 1.5 H₂O is isostructural with K₂CO₃ · 1.5 H₂O. In case of Cs₂CO₃ · 3 H₂O no comparable structure is known. Both structures show [(CO₃^2–)(H₂O)]‐chains, being connected via additional H₂O forming columns (Rb₂CO₃ · 1.5 H₂O) and layers (Cs₂CO₃ · 3 H₂O), respectively.     

Synthese und Kristallstruktur von Y(HSO4)3-I und Y(HSO4)3 · H2O

Syntheses and Crystal Structures of Y(HSO₄)₃-I and Y(HSO₄)₃ · H₂O Lath shaped crystals of Y(HSO₄)-I are obtained by treatment of Y₂O₃ with conc. sulfuric acid at 200 °C. Y(HSO₄)₃-I crystallizes orthorhombic (Pbca, Z = 8, a = 1201.5(1), b = 953.76(8), c = 1650.4(1) pm, R_all = 0.0388). In the crystal structure Y³⁺ is coordinated by eight monodentate HSO₄^– groups. Colorless, plate like single crystals of Y(HSO₄)₃ · H₂O grew from a solution of Y₂O₃ in 85% sulfuric acid upon cooling. In the crystal structure of the triclinic compound (P1, Z = 2, a = 679.8(1), b = 802.8(2), c = 965.9(2) pm, α = 79.99(2)°, β = 77.32(2)°, γ = 77.50(2)°, R_all = 0.0264) Y³⁺ is surrounded by seven HSO₄^– groups and one molecule of water.     

Synthese und Kristallstruktur von [(PhCH2)2GaF(tBuNH2)]2 · 2 THF

Synthesis and Crystal Structure of [(PhCH₂)₂GaF(^tBuNH₂)]₂ · 2 THF (PhCH₂)₂GaF reacts with ^tBuNH₂ to the adduct [(PhCH₂)₂GaF(^tBuNH₂)] ( 1 ). 1 was characterized by NMR, IR and MS techniques. 1 can be recrystallized from THF forming crystals of [ 1 ]₂ · 2 THF. According to an X-ray structure analysis [ 1 ]₂ · 2 THF consists of dimers of 1 formed by hydrogen bridges. The THF molecules are coordinated to [ 1 ]₂ by hydrogen bridges, too.     

Synthese und Kristallstruktur der Übergangsmetalltrimetaphosphimate Zn3[(PO2NH)3]2 · 14 H2O und Co3[(PO2NH)3]2 · 14 H2O

Synthesis and Crystal Structure of the Transition Metal Trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O The transition metal trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O were obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with the respective metal nitrate or halide (molar ratio 1 : 4). The structure of Zn₃[(PO₂NH)₃]₂ · 14 H₂O was solved by single crystal X‐ray methods. The structure of isotypic Co₃[(PO₂NH)₃]₂ · 14 H₂O was refined from X‐ray powder diffraction data using the Rietveld method (Zn₃[(PO₂NH)₃]₂ · 14 H₂O ( 1 ): P 1, a = 743.7(2), b = 955.9(2), c = 980.1(2) pm, α = 102.70(3), β = 90.46(3), and γ = 100.12(3)°, Z = 1; Co₃[(PO₂NH)₃]₂ · 14 H₂O ( 2 ): P 1, a = 746.05(1), b = 957.06(2), c = 988.51(2) pm, α = 102.162(1), β = 90.044(1), and γ = 99.258(1)°, Z = 1). In 1 and 2 the P₃N₃ rings of the trimetaphosphimate ions attain a conformation which can be described as a combination of an ideal boat and an ideal twist conformation. The trimetaphosphimate ions act as bridging ligands. Thus chains of alternating M²⁺ and (PO₂NH)₃^3– ions are formed which are interconnected by additional M²⁺ ions forming electro‐neutral double chains. In the solid these double chains are connected by hydrogen bonds.     

Die Kristallpackung von (PPh4)2[NiCl4] · 2 MeCN und PPh4[CoCl0,6Br2,4(NCMe)]

The Crystal Packings of (PPh₄)₂[NiCl₄] · 2 MeCN and PPh₄[CoCl_0.6Br_2.4(NCMe)] (PPh₄)₂[NiCl₄] · 2 MeCN was obtained from the reaction of PPh₄Cl and NiCl₂ in acetonitrile in the presence of S₂Cl₂, PPh₄[Cl₂H] being a side product. The product of the reaction of CoS₂ with S₂Br₂ (containing rests of S₂Cl₂) at 400 °C was treated with PPh₄Br in acetonitrile yielding PPh₄Br₃ and PPh₄[CoCl_0.6Br_2.4(NCMe)]. The crystal structures of the title compounds were determined by X‐ray diffraction. (PPh₄)₂[NiCl₄] · 2 MeCN (space group I 4, a = 1839.3 pm, c = 1375.3 pm) has a crystal packing derived from the BiPh₄[ClO₄] structure type with a fourfold increased unit cell and one half of the ClO₄^– positions substituted by pairsof acetonitrile molecules. The crystal structure of PPh₄[CoCl_0.6Br_2.4(NCMe)] (space group I4₁/a, a = 1804.7 pm, c = 3198.8 pm) is related to the AsPh₄[RuNCl₄] type with an eightfold increased unit cell. The [CoCl_0.6Br_2.4(NCMe)]^– ions are disordered in two orientations and some halogen positions are randomly occupied by Cl and Br atoms. Family trees of group–subgroup relations show the symmetry relations.     

Darstellung,Schwingungsspektren und Kristallstrukturen von [(Ph3P)2N]2[(W6Cl)I] · 2 Et2O · 2 CH2Cl2 und [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph₃P)₂N]₂[(W₆Cl )I ] · 2 Et₂O · 2 CH₂Cl₂ and [(Ph₃P)₂N]₂[(W₆Cl )(NCS) ] · 2 CH₂Cl₂ By treatment of [(W₆Cl)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W₆Cl)(NCS)]^2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph₃P)₂N]₂[(W₆Cl)I] · 2 CH₂Cl₂ · 2 Et₂O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph₃P)₂N]₂[(W₆Cl)(NCS)] · 2 CH₂Cl₂ ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (ν_CN), 879–867 (ν_CS) and 490–482 (δ_NCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu₄N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are f_d(WW) = 1.61, f_d(WI) = 1.23 and f_d(WCl) = 1.10 mdyn/Å.     

[(C2H5)3NH]2Sn3Se7 · 0,25 H2O und [(C3H7)2NH2]4Sn4Se10 · 4 H2O

Synthesis, Structure, and Properties of Some Selenidostannates. II. [(C₂H₅)₃NH]₂Sn₃Se₇ · 0,25 H₂O and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O The new selenidostannate hydrates [(C₂H₅)₃NH]₂Sn₃Se₇ · 0.25 H₂O ( I ) and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O ( II ) were synthesized from an aqueous suspension of triethylammonium (tripropylammonium), tin, selenium I and in addition sulfur II at 130 °C. I crystallizes at ambient temperature in the monoclinic space group P2₁/n (a = 2069,3(4) pm, b = 1396,6(3) pm, c = 2342,8(5) pm, β = 114,68(3)°, Z = 8) and is characterized by two different anions, chains from edge‐sharing [Se₃Se₇]^2– units and nets from trigonal SnSe₅ bipyramids. II crystallizes at ambient temperature in the tetragonal space group I4₁/amd (a = 2150,0(3) pm, c = 1174,4(2) pm, Z = 4) and contains adamantane like [Sn₄Se₁₀]^4–‐cages. The UV‐VIS spectra of the selenidostannates demonstrate that the absorption edges red shift as the dimensionality of the compounds is increased.     

Reaction of the Pincer‐type Ligand {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu‐C6H2}— with [Ph3C]+[PF6]—. Unprecedented Rearrangement and Carbon‐Carbon Bond Formation

The reaction of the organolithium derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu‐C₆H₂}Li ( 1 ‐Li) with [Ph₃C]⁺[PF₆]^— gave the substituted biphenyl derivative 4‐[(C₆H₅)₂CH]‐4′‐[tert‐Bu]‐2′, 6′‐[P(O)(OEt)₂]₂‐1, 1′‐biphenyl ( 5 ) which was characterized by ¹H, ¹³C and ³¹P NMR spectroscopy and single crystal X‐ray analysis. Ab initio MO‐calculations reveal the intramolecular O···C distances in 5 of 2.952(4) and 2.988(5)Å being shorter than the sum of the van der Waals radii of oxygen and carbon to be the result of crystal packing effects. Also reported are the synthesis and structure of the bromine‐substituted derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu]C₆H₂}Br ( 9 ) and the structure of the protonated ligand 5‐tert‐Bu‐1, 3‐[P(O)(OEt)₂]₂C₆H₃ ( 1 ‐H). The structures of 1 ‐H, 5 , and 9 are compared with those of related metal‐substituted derivatives.