Darstellung und Kristallstruktur von Ptl3, einem valenzgemischten Platin (II,IV)-iodid

Preparation and Crystal Structure of PtI₃, a Mixed-valence Platinum (II, IV) Iodide PtI₃ was obtained by thermal decomposition of PtI₄ in a closed system at 300°C and 8 atm iodine pressure. Single crystals were formed by the reaction of PtI₄ with aqueous solutions of KI and I₂ at 270°C. The crystal structure of the monoclinic compound (a = 673.5(2) pm; b = 1206.1(4) pm; c = 1331.3(5) pm; β = 101.25(6)°; Z = 8; space group C2/c-C_2h⁶) contains square planar PtI₄ and octahedral PtI₆ groups which are connected by common edges to chains.     

Molekulare gemischtvalente Platin-Iod-Amin-Komplexe: Das dreikernige Pt3I8(NHEt2)2 mit kantenverknüpften planaren und oktaedrischen Baugruppen

Mixed Valence Molecular Platinum Iodide Amin Complexes: The Trinuclear Pt₃I₈(NHEt₂)₂ with Edgeshared Planar and Octahedral Building Groups PtI₂ · NHEt₂ was prepared by reaction of K₂PtCl₄ with KI and NEt₂H in aqueous solution. The crystal structure of the monoclinic compound (a = 20.558(4) Å; b = 7.254(1) Å; c = 13.790(3) Å; β = 100.47(3)°; space group C2/c) consists of binuclear molecules of [{Pt(NH(Et)₂)I}₂(μ-I)₂]. On oxidation of this Pt(II) compound by I₂ in CH₂Cl₂ mixtures of the trinuclear mixed-valence compound Pt₃I₈(NHEt₂)₂ and of the binuclear Pt^IV complex [{Pt(NHEt₂)I₃}₂(μ-I)₂] were obtained. The monoclinic crystal structure of Pt₃I₈(NHEt₂)₂ (a = 20.278(4) Å; b = 10.627(2) Å, c = 14.232(3) Å; β = 115.66(3)° space group C2/c) is built up by trimeric units of two planar Pt^III₃(NHEt₂) groups sharing edges with a central Pt^IVI₆-octhedron.     

Darstellung und Charakterisierung von Iodoplatinaten MexNH4–xPtI4 (x = 2 − 4), gemischtvalenten Octaiododiplatinaten(II,IV) mit Pt2I8-Baugruppen

Preparation and Characterization of Iodoplatinates Me_xNH_4–xPtI₄ (x = 2–4), Mixed Valence Octaiododiplatinates(II,IV) with Pt₂I₈ Groups Iodoplatinates APtI₄ (A = Me_xNH_4–x with x = 2–4) have been prepared by partial oxidation of the correspondent hexaiododiplatinates(II) A₂Pt₂I₆ with I₂ in methanolic solutions. X-ray structure analyses of the bronze-coloured needle-shaped crystals of the compounds showed rows of dinuclear anions Pt₂I₈^2?, built up by edgesharing planar PtI₄ groups with Pt^II und octahedral PtI₆ groups with Pt^IV. The different space requirement of the cations leads to the formation of three different structures. Within the anion stacks weak intermolecular Pt^IV? I …? Pt^II interactions are detectable by Raman spectroscopy.     

Synthese,Eigenschaften und Struktur von LiAuI4 und KAuI4 mit einer Diskussion der kristallchemischen Verwandtschaft zwischen den Halogenoauraten RbAuCl4, AgAuCl4, RbAuBr4 und LiAuI4

Synthesis, Properties, and Structure of LiAuI₄ and KAuI₄ with a Discussion of the Crystal Chemical Relationship between the Halogenoaurates RbAuCl₄, AgAuCl₄, RbAuBr₄ and LiAuI₄ The alkalimetal iodo aurates(III) MAuI₄ (M ? Li, K) are obtained in form of single crystals from MI, Au and I₂ in a sealed glass ampoule by heating to 550°C and slow cooling to 300°C. KAuI₄ crystallizes in the monoclinic space group P2₁/c with a = 968.6(4); b = 704.5(2), c = 1393.2(7) pm; β = 100.95(2)° and Z = 4. The crystal structure is built up from square planar AuI₄^? anions and K⁺ cations. The cations are coordinated by eight I atoms of neighbouring AuI₄^? anions with distances K? I between 350.0 and 369.6 pm. At 100°C KAuI₄ is reduced to form K₃Au₃I₈, which at 180°C decomposes to KI, Au and I₂ LiAuI₄ forms black, moisture sensitive needles, decomposing in the absence of iodine at 20°C to LiI, Au and I₂. It crystallizes in a variant of the RbAuBr₄ type structure with the space group P2₁/a and a = 1511.7(4); b = 433.9(4); c = 710.0(2) pm; β = 121.50(2)°; Z = 2. The crystal chemical relationship between the structures of RbAuCl₄, RbAuBr₄, AgAuCl₄ and LiAuI₄ is discussed.     

Bi13Pt3I7: Ein Subiodid mit einer pseudosymmetrischen Schichtstruktur

Bi₁₃Pt₃I₇: A Subiodide with a Pseudo-Symmetric Layer Structure The reaction of PtI₂ with Bi and BiI at 630 K yields black, lustrous, air insensitive crystals of the subiodide Bi₁₃Pt₃I₇. The layered crystal structure (triclinic, C1 , a = 1581.0(2) pm, b = 912.6(1) pm, c = 2149.6(6) pm, α = 90.03(2)°, β = 96.96(2)°, γ = 90.11(1)°, V = 3078.6 · 10⁶ pm³) contains edge-sharing [PtBi_8/2] cubes, which form nets of Kagomé type. Iodine atoms fill the hexagonal-prismatic voids therein. These [(PtBi_8/2)₃I] layers are alternately separated by layers of iodine atoms or [BiI] zigzag-chains. The marked pseudo-symmetry of the structure favours stacking faults, which cause streaks of diffuse scattering in the diffraction pattern.     

A one‐dimensional iodine‐bridged PtII/PtIV mixed‐valence complex,catena‐poly[[[bis­(ethyl­ene­diamine)­platinum(II)]‐μ‐iodo‐[bis­(ethyl­ene­di­amine)platinum(IV)]‐μ‐iodo] hydrogenphosphate dihydrogenphosphate iodide trihydrate]

The title compound, {[Pt^IIPt^IVI₂(C₂H₈N₂)₄](HPO₄)(H₂PO₄)I·3H₂O}_n, has a chain structure composed of square‐planar [Pt(en)₂]²⁺ and elongated octa­hedral trans‐[PtI₂(en)₂]²⁺ cations (en is ethyl­ene­diamine) stacked alternately along the c axis and bridged by the I atoms; a three‐dimensionally valence‐ordered system exists with respect to the Pt sites. The title compound also has a unique cyclic tetra­mer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions connected by strong hydrogen bonds [O⋯O = 2.522 (10), 2.567 (10) and 2.569 (11) Å]. The Pt and I atoms form a zigzag ⋯I—Pt^IV—I⋯Pt^II⋯ chain, with Pt^IV—I bond distances of 2.6997 (7) and 2.6921 (7) Å, inter­atomic Pt^II⋯I distances of 3.3239 (8) and 3.2902 (7) Å, and Pt^IV—I⋯Pt^II angles of 154.52 (3) and 163.64 (3)°. The structural parameters indicating the mixed‐valence state of platinum, expressed by δ = (Pt^IV—I)/(Pt^II—I), are 0.812 and 0.818 for the two independent I atoms.     

Eine neue Methode zur Messung von temperaturabhängigen Partialdrücken in geschlossenen Systemen. Die Bestimmung der Bildungsenthalpie und -entropie von PtI2(s)

Determination of Temperature Dependent Partial Pressures in Closed Systems – a New Method. The Heat of Formation for PtI₂(s) A new method to determine temperature dependent partial pressures of gaseous species in equilibria with condensed phases in closed systems (silica ampoules) at temperatures up to 1000 °C and pressures p_i 0.01 < p_i < 10 bar is presented. It is based on the determination of the change of mass in the gasphase caused by solid-gas transition at higher temperatures of substances which are deposited at one end of the ampoule. The results of the measurements give informations about reaction mechanisms, enthalpies and entropies. The reliability of the method is demonstrated at the example of the system Pt/I₂. The heat of formation and the entropy of PtI₂(s) (δ_BH°(PtI₂(s), 298) = –51.4 kJ · mol^–1, S°(PtI₂(s), 298) = 119.3 J · K^–1 · mol^–1) are computed from experimental results. The heat of thermal decomposition of PtI₂(s) was reconsidered by Knudsen Mass Spectrometry.     

Synthesis,Characterization and Crystal Structures of new Palladium(II) Complexes and the first Platinum(III) Complex Containing ATT (ATT = 6‐Aza‐2‐thiothymine)

Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL)₄Pd]Cl₂·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans‐[(HL)₂PdI₂]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na₂[PdCl₄] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L₄Pd₂)NaCl]₂·8MeOH ( 4 ) and [L₄Pt₂Cl₂]·6MeOH·H₂O ( 5 ). The latter is the first Pt^III complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: triclinic space group , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R₁ = 0.0278; for 3 at ?80 °C: triclinic space group , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R₁ = 0.0394; for 4 at ?80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R₁ = 0.0341 and for 5 at ?80 °C: monoclinic space group P2₁/c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R₁ = 0.0429.     

Untersuchungen an Polyhalogeniden. XVI. Darstellung und Kristallstrukturen der Bipyridiniumpolyiodide Bipy · HIn mit n = 3, 5 und 7

Studies on Polyhalides. 16. Preparation and Crystal Structures of Bipyridiniumpolyiodides Bipy · HI_n with n = 3, 5, and 7 With simply protonated α,α′-Bipyridyl Bipy · H⁺ a triiodide Bipy · HI₃, a pentaiodide Bipy · HI₅ and a heptaiodide Bipy · HI₇ may be prepared in the presence of iodide ions I^? and dependent of the iodine I₂ content. Bipyridiniumtriiodide C₁₀H₉N₂I₃ crystallizes at room temperature monoclinically in P2₁/n with a = 1 122.8(1) pm, b = 1 072.7(1) pm, c = 1 200.2(3) pm, β = 98.02(2)° and Z = 4. The crystal structure is built up from mixed cationic and anionic layers. Bipyridiniumpentaiodide C₁₀H₉N₂I₅ crystallizes at room temperature monoclinically in P2₁/c with a = 887.3(5) pm, b = 2 527.9(12) pm, c = 830.7(3) pm, β = 106.78(5)° and Z = 4. The crystal structure contains triiodide ions I₃^? till now uniquely connected by iodine molecules I₂ in a trigonal planar way. Bipyridiniumheptaiodide C₁₀H₉N₂I₇ crystallizes at room temperature triclinically in P&1macr; with a = 713.1(3) pm, b = 1 007.9(3) pm, c = 1 464,8(4) pm, α = 81.07(3)°, β = 89.92(3)°, γ = 82.77(3)° and Z = 2. The crystal structure contains a V-shaped pentaiodide ion I₅^? completed by an iodine molecule I₂ to a trigonal pyramidally shaped heptaiodide ion I₇^? and at the same time connected to a zigzag chain.     

Synthesis and Crystal Structure of AgCuVO4

Dark red single crystals of AgCuVO₄ were obtained from hydroxide fluxes in Ag‐containers at 430 °C. According to X‐ray diffraction data AgCuVO₄ crystallizes in the orthorhombic space group Pnma (Z = 4, a = 925.5(1) pm, b = 677.8(1) pm, c = 540.1(1) pm, wR2 = 0.0753). The Pearson code (oP28) and Wyckoff sequence (dc⁴a) indicate that AgCuVO₄ is related to the olivine‐type of structure, but the first coordination sphere of Ag^I and Cu^II differ significantly from the C.N. 6 with irregular square‐pyramidal [AgO₅] polyhedra and distorted square‐planar [CuO₄] units. These differences in crystal chemistry are discussed and MAPLE as well as ECoN values are given.     

Untersuchungen an Polyhalogeniden III. Tetrammin-kupfer(II)-tetraiodid, [Cu(NH3)4I2 · I2], und Tetrammin-kupfer(II)-hexaiodid, [Cu(NH3)4I3]I3

Studies on Polyhalides. III. Crystal Structures of [Cu(NH₃)₄I₂ · I₂] and [Cu(NH₃)₄I₃]I₃ Tetramminecopper(II)tetraiodide [Cu(NH₃)₄I₂ · I₂] (I) crystallizes monoclinically in the space group C2/m with a = 1 185.9 pm, b = 892.8 pm, c = 656.8 pm, β = 111.10° and Z = 2 formula units. Tetramminecopper(II)hexaiodide [Cu(NH₃)₄I₃]I₃ (II) crystallizes orthorhombically in the space group Pnnm with a = 874.9 pm, b = 1 089.8 pm, c = 885.3 pm, and Z = 2 formula units. A special feature of these structures are coordinated polyiodide ions I₄^2? (I) or I₃^? (II). In both compounds four coplanar nitrogen atoms and two axial iodine atoms form a quasi-octahedral coordination around copper with the usual (4+2)-tetragonal distortion. The copper ions are connected by linear, centrosymmetric polyiodide ions I₄^2? (I) or I₃^? (II). Therefore infinite planar zigzag chains of units [Cu(NH₃)₄I₄] (I) or [Cu(NH₃)₄I₃]⁺(II) are resulting. The counterion I₃^? (II) is intercalated between these chains.     

Ga8Ir4B – ein Gallium-Iridiumborid mit isolierten,annähernd quadratisch planaren Ir4B-Gruppen in einer vom CaF2-Typ abgeleiteten Struktur

Ga₈Ir₄B – a Gallium Iridium Boride with isolated, nearly square planar Ir₄B Groups in a Structure derived from the CaF₂ Type The new compound Ga₈Ir₄B (tetragonal, I4₁/acd, a = 853.69(2) pm, c = 2 105.69(6) pm, Z = 8, 614 reflections, 31 parameters, R = 0.034) was prepared by reaction of the elements at 1 100°C. The structure is derived from the CaF₂ type. It contains isolated Ir₄B groups with boron in an unusual, nearly square planar coordination.     

Über die Decamethylferroceniumpolyiodide [(Me5C5)2Fe]Ix mit x = 3, 5 und 6,5. Darstellung und strukturelle Charakterisierung eines Triiodids (DMFc)I3, eines Pentaiodids (DMFc)I5 und eines Hexacosaiodids (DMFc)4I26

Studies on Polyhalides. 30 On Decamethylferriciniumpolyiodides [(Me₅C₅)₂Fe]I_x with x = 3, 5, 6.5: Preparation and Crystal Structures of a Triiodide (DMFc)I₃, a Pentaiodide (DMFc)I₅ and a Hexacosaiodide (DMFc)₄I₂₆ Decamethylferrocene (DMFc) may be oxidized by iodine analogous to ferrocene (Fc) to the decamethylferrocenium ion (DMFc)⁺ and precipitated as the crystalline solids decamethylferrocenium triiodide (DMFc)I₃, decamethylferrocenium pentaiodide (DMFc)I₅ and tetracisdecamethylferrocenium hexacosaiodide (DMFc)₄I₂₆. The two compounds with higher iodine content are new. These are characterized by X-ray diffraction methods on single crystals. The structures are built up from complex cations of expected geometry and isolated or remarkably connected polyiodide ions. Decamethylferrocenium triiodide C₂₀H₃₀FeI₃ crystallizes monoclinically in C2/m with a = 1489.9(4) pm, b = 1133.0(2) pm, c = 765.9(3) pm, β = 111.76(3)° and Z = 2. The crystal structure follows the CsCl-type and contains isolated triiodide ions of the linear symmetric form. Decamethylferrocenium pentaiodide C₂₀H₃₀FeI₅ crystallizes monoclinically in P2₁/c with a = 1130.0(2) pm, b = 1442.6(1) pm, c = 1716.6(2) pm, β = 96.62(1)° and Z = 4. The crystal structure may be deduced from the primitiv quadratic bundle of alternating cationic and anionic rods. It contains exceptionally isolated somewhat opened out pentaiodide ions. Tetrakisdecamethylferrocenium hexacosaiodide (C₂₀H₃₀Fe)₄I₂₆ crystallises monoclinically in P2₁/n with a = 1331.3(8) pm, b = 1319.4(4) pm, c = 3564(2) pm, β = 90.84(5)° and Z = 2. The crystal structure of this compound with unusual composition may be described as an inclusion compound with channels for the cations. The outstanding anionic grating may be derived from the primitive cubic lattice of iodide ions with iodine bridges on all edges by removing systematically 1/12 of the iodine molecules.     

Synthese und Struktur der Platin(O)-Verbindungen [(dipb)Pt]2(COD) und (dipb)3Pt2 sowie des clusters Hg6[Pt(dipb)]4 (dipb = (i-Pr)2P(CH2)4P(i-Pr)2)

Synthesis and Structure of the Platinum(0) Compounds [(dipb)Pt]₂(COD) and (dipb)₃Pt₂ and of the Cluster Hg₆[Pt(dipb)]₄ (dipb = (i-Pr)₂P(CH₂)₄P(i-Pr)₂) The reduction of (dipb)PtCl₂ with Na/Hg yields (dipb)Pt as an intermediate which reacts with the amalgam to form the cluster Hg₆[Pt(dipb)]₄ ( 3 ) or decomposes to (dipb)₃Pt₂ ( 2 ) and Pt. In the presence of COD [(dipb)Pt]₂(COD) ( 1 ) is obtained. 1 crystallizes monoclinicly in the space group P2₁/c with a = 1596.1(4), b = 996.5(2), c = 1550.4(3) pm, β = 113.65(2)°, Z = 2. In the dinuclear complex two (dipb)Pt units are bridged by a 1,2-η²-5,6-η² bonded COD ligand. Whereby the C = C double bonds are lengthened to 145 pm. 2 forms triclinic crystals with the space group P1 and a = 1002.0(2), b = 1635.9(3), c = 868.2(2) pm, α = 94.70(2)°, β = 94.45(2)°, σ = 87.95(1)°, Z = 1. In 2 two (dipb)Pt moieties are connected by a μ-dipb ligand in a centrosymmetrical arrangement. 3 is monoclinic with the space group C2/c and a = 1273.8(3), b = 4869.2(6), c = 1660.2(3) pm, β = 95.16(2)°, Z = 4. The clusters Hg₆[Pt(dipb)]₄ have the symmetry C₂. Central unit is a Hg₆ octahedron of which four faces are occupied by Pt(dipb) groups. The bonding in the cluster is discussed on the basis of eight Pt? Hg two center bonds of 267.6 pm and two Pt? Hg? Pt three center bonds with Pt? Hg = 288.0 pm.     

Untersuchungen an Polyhalogeniden. XXIII. Kristallstrukturen der N-Alkylurotropiniumtriiodide UrRI3 mit R = Methyl,Ethyl, n-Propyl und n-Butyl

Studies on Polyhalides. 23. Crystal Structures of N-Alkylurotropinium Triiodides UrRI₃ with R = Methyl, Ethyl, n-Propyl, and n-Butyl The salts UrRI₃ may be prepared by the reaction of N-alkylurotropinium iodides UrRI with iodine I₂ at room temperature from aqueous solution. N-methylurotropinium triiodide C₇H₁₅N₄I₃ crystallizes monoclinically in P2₁/c with a = 1300.8(2) pm, b = 1276.0(3) pm, c = 859.3(2) pm, β = 94.75(2)° and Z = 4. The crystal structure is built up from layers of cations UrMe⁺ and of linear symmetric triiodide ions I₃^? alternating along [100]. N-ethylurotropinium triiodide C₈H₁₇N₄I₃ crystallizes orthorhombically in Pnma with a = 1397.3(5) pm, b = 1221.3(2) pm, c = 886.2(2) pm and Z = 4. The cationic (UrEt⁺) and anionic (I₃^?) layers alternate along [0 10]. N-propylurotropinium triiodide C₉H₁₉N₄I₃ crystallizes monoclinically in P2₁/c with a = 1885.7(5) pm, b = 1657.1(5) pm, c = 1700.5(4) pm, β = 112.39(2)° and Z = 12. The three independent cations and anions are slightly, but differently distorted. N-butylurotropinium triiodide C₁₀H₂₁N₄I₃ crystallizes monoclinically in P2₁/m with a = 991.8(3) pm, b = 757.8(2) pm, c = 1128.2(2) pm, β = 90.73(2)° and Z = 2. The crystal structure is stacked by alternating cationic and anionic layers along [001]. The triiodide ion is asymmetric and linear.     

Cs4[IrO4], ein neues Iridat mit planarem Anion [IrO4]4−

Cs₄[IrO₄], a New Iridate with Planar Anion [IrO₄]^4? For the first time we obtained black single crystals of Cs₄[IrO₄] by heating intimate mixtures of CsO_0.52 and IrO₂ (molar ratio Cs : Ir = 4.30 : 1.00; “Ag-bomb”, 740°C/86 d). Cs₄[IrO₄] crystallizes monocline, C 2/m, with a = 1031.66(8) pm, b = 671.61(4) pm, c = 660.44(6) pm, b? = 108.118(7)° and Z = 2 in the K₄[IrO₄]-type. The structure has been determined by four-circle-diffractometer data (PW 1100 from Phillips, Ag? Kα , graphite) with 841 I₀(hkl) with I ≥ 3s?(F) (from 947 I₀(hkl) out of 3529 measured reflexes). The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Intercalation von Metallnitraten in Graphit. IV. Die Reaktion von wasserfreiem Kupfer(II)-nitrat mit Graphit

Intercalation of Metal Nitrates in Graphite. IV. Reaction of Anhydrous Copper (II) Nitrate with Graphite By heating of Cu(NO₃)₂ and Cu(NO₃)₂ · N₂O₄ with graphite (160–200°C, 1–8 d) samples of stage 4, 5, and 6 of Cu(NO₃)₂ graphite were obtained, which were characterized by X-ray powder diffraction and chemical analysis. 4^th stage: I_c = 2030 pm, C:Cu ≈ 40:1. 5^th stage: I_c = 2365 pm, C:Cu ≈ 50:1. 6^th stage: I_c = 2700 pm, C:Cu ≈ 60:1. The intercalate thickness was found to be 690 pm. Heating with Cl₂ yields the corresponding stages of CuCl₂ graphite.     

[M9C4O]I8 (M = Y,Ho, Er,Lu), reduzierte Selten-Erd-Iodide mit gewellten Metall-Doppelschichten und zwei verschiedenen interstitiellen Atomen

[M₉C₄O]I₈ (M = Y, Ho, Er, Lu), Reduced Rare-Earth Iodides with Waved Metal Double Layers and Two Different Interstitial Atoms [M₉C₄O]I₈ (M = Y, Ho, Er, Lu) are examples of reduced rare-earth iodides with two different interstitial atoms. The compounds were synthesized from appropriate mixtures of MI₃, M, C and M₂O₃ at 1 050°C in arc-welded tantalum containers. The X-ray structure analysis of a single crystal of [Y₉C₄O]I₈ (orthorhombic, Pmmn (Nr. 59), Z = 2, a = 2 912.7(6) pm, b = 384.17(4) pm, c = 1 080.29(9) pm, R = 0.084, R_w = 0.053) exhibits octahedrally coordinated carbon in “plane” sections besides tetrahedrally coordinated oxygen in the “bend” of waved metal double layers. These double layers are stacked alternately with waved iodine double layers along [001].     

Phosphaniminato-Komplexe des Iods. Synthese und Kristallstrukturen von Ph3PNIO2 und Ph3PNSiMe3 · I2

Phosphoraneiminato Complexes of Iodine. Syntheses and Crystal Structures of Ph₃PNIO₂ and Ph₃PNSiMe₃ · I₂ Ph₃PNIO₂ has been prepared as yellow crystals by the reaction of Ph₃PNSiMe₃ with I₂O₅ in boiling acetonitrile, whereas the molecular complex Ph₃PNSiMe₃ · I₂ is formed as brown crystals by the reaction of Ph₃PNSiMe₃ with iodine in acetonitrile solution. Both complexes were characterized by crystal structure determinations. Ph₃PNIO₂: Space group P2₁/n, Z = 4, 2 858 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 972.8(2), b = 1 743.4(3), c = 1 073.7(2) pm, β = 115.46(3)°. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9°) is unusually small; the PN bond length of 159.2 pm corresponds with a double bond. Ph₃PNSiMe₃ · I₂: Space group P1 , Z = 2, 3 560 observed unique reflections, R = 0.033. Lattice dimensions at 19°C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, α = 78.34(1)°, β = 72.00(2)°, γ = 86.08(2)°. The compound forms monomeric molecules, in which the I₂ molecule and the nitrogen atom of the phosphoraneimine molecule realize a linear N? I? I axis with a bond length N? I of 243.2 pm.     

Die Kristallstrukturen einer Serie von Verbindungen mit Kationen des Typs [R3PNH2]+, [R3PN(H)SiMe3]+ und [R3PN(SiMe3)2]+

Crystal Structures of a Series of Compounds with Cations of the Type [R₃PNH₂]⁺, [R₃PN(H)SiMe₃]⁺, and [R₃PN(SiMe₃)₂]⁺ The crystal structures of a series of compounds with cations of the type [R₃PNH₂]⁺, [R₃PN(H)SiMe₃]⁺, and [R₃PN(SiMe₃)₂]⁺, in which R represents various organic residues, are determined by means of X‐ray structure analyses at single crystals. The disilylated compounds [Me₃PN(SiMe₃)₂]⁺I^–, [Et₃PN(SiMe₃)₂]⁺I^–, and [Ph₃PN(SiMe₃)₂]⁺I₃^– are prepared from the corresponding silylated phosphaneimines R₃PNSiMe₃ with Me₃SiI. [Me₃PNH₂]Cl (1): Space group P2₁/n, Z = 4, lattice dimensions at –71 °C: a = 686.6(1), b = 938.8(1), c = 1124.3(1) pm; β = 103.31(1)°; R = 0.0239. [Et₃PNH₂]Cl (2): Space group Pbca, Z = 8, lattice dimensions at –50 °C: a = 1272.0(2), b = 1147.2(2), c = 1302.0(3) pm; R = 0.0419. [Et₃PNH₂]I (3): Space group P2₁2₁2₁, Z = 4, lattice dimensions at –50 °C: a = 712.1(1), b = 1233.3(2), c = 1257.1(2) pm; R = 0.0576. [Et₃PNH₂]₂[B₁₀H₁₀] (4): Space group P2₁/n, Z = 4, lattice dimensions at –50 °C: a = 809.3(1), b = 1703.6(1), c = 1800.1(1) pm; β = 96.34(1)°; R = 0.0533. [Ph₃PNH₂]ICl₂ (5): Space group P1, Z = 2, lattice dimensions at –60 °C: a = 825.3(3), b = 1086.4(3), c = 1241.2(4) pm; α = 114.12(2)°, β = 104.50(2)°, γ = 93.21(2)°; R = 0.0644. In the compounds 1–5 the cations are connected with their anions via hydrogen bonds of the NH₂ groups with 1–3 forming zigzag chains. [Me₃PN(H)SiMe₃][O₃S–CF₃] (6): Space group P2₁/c, Z = 8, lattice dimensions at –83 °C: a = 1777.1(1), b = 1173.6(1), c = 1611.4(1) pm; β = 115.389(6)°; R = 0.0332. [Et₃PN(H)SiMe₃]I (7): Space group P2₁/n, Z = 4, lattice dimensions at –70 °C: a = 1360.2(1), b = 874.2(1), c = 1462.1(1) pm; β = 115.19(1)°; R = 0.066. In 6 and 7 the cations form ion pairs with their anions via NH … X hydrogen bonds. [Me₃PN(SiMe₃)₂]I (8): Space group P2₁/c, Z = 8, lattice dimensions at –60 °C: a = 1925.4(9), b = 1269.1(1), c = 1507.3(4); β = 111.79(3)°; R = 0.0581. [Et₃PN(SiMe₃)₂]I (9): Space group Pbcn, Z = 8, lattice dimensions at –50 °C: a = 2554.0(2), b = 1322.3(1), c = 1165.3(2) pm; R = 0.037. [Ph₃PN(SiMe₃)₂]I₃ (10): Space group P2₁, Z = 2, lattice dimensions at –50 °C: a = 947.7(1), b = 1047.6(1), c = 1601.6(4) pm; β = 105.96(1)°; R = 0.0334. 8 to 10 are built up from separated ions.