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.     

Untersuchungen an Polyhalogeniden. XXII [1]. Dimethyldiphenylammoniumpolyiodide (Me2Ph2N)In mit n = 3, 13/3, 6, 8: Darstellung und strukturelle Charakterisierung eines Triiodids (Me2Ph2N)I3, Tridecaiodids (Me2Ph2N)3I13, Dodecaiodids (Me2Ph2N)2I12 und Hexadecaiodids (Me2Ph2N)2I16

Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me₂Ph₂N)I_n with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me₂Ph₂N)I₃, Tridecaiodide (Me₂Ph₂N)₃I₁₃, Dodecaiodide (Me₂Ph₂N)₂I₁₂, and Hexadecaiodide (Me₂Ph₂N)₂I₁₆ The new compounds [(CH₃)₂(C₆H₅)₂N]I₃, [(CH₃)₂(C₆H₅)₂N]₃I₁₃, [(CH₃)₂(C₆H₅)₂N]₂I₁₂ and [(CH₃)₂(C₆H₅)₂N]₂I₁₆ have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH₃)₂(C₆H₅)₂N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure.     

Zur Struktur zweier Isothiazolium‐Polyiodide (C19H16FeNS)I5 und (C15H12NS)2I8

On the Structure of Two Isothiazolium Polyiodides (C₁₉H₁₆FeNS)I₅ and (C₁₅H₁₂NS)₂I₈ By oxidation of 3‐phenylamino thiopropenones with iodine two isothiazolium polyiodides were obtained, whose structures have been determined by X‐ray structure analysis. 2‐Phenyl‐5‐ferrocenyl‐isothiazolium pentaiodide(C₁₉H₁₆FeNS)I₅ forms a layer structure with isothiazolium cations and polyiodide anions. The polyiodide layers contain pentaiodide ions I₅^–, triiodide ions I₃^– and iodine molecules I₂. Bis(2,5‐diphenyl‐isothiazolium) octaiodide (C₁₅H₁₂NS)₂I₈ also forms a layer structure with isothiazolium cations and polyiodide anions. The polyiodide layers are built up by octaiodide ions I₈^2–, pentaiodide ions I₅^– and triiodide ions I₃^–.     

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.     

[Ba(Benzo‐15‐Krone‐5)2](In)2: Darstellung und strukturelle Charakterisierung eines Triiodids (n = 3) und eines Heptaiodids (n = 7)

[Ba(benzo‐15‐crown‐5)₂](I₃)₂ and [Ba(benzo‐15‐crown‐5)₂](I₇)₂ can be obtained in crystalline form by reacting benzo‐15‐crown‐5 (C₁₄H₂₀O₅), barium iodide (BaI₂), and iodine (I₂) in ethan‐ole /dichloromethane. The triiodide consists of a sandwich‐like cation [Ba(benzo‐15‐crown‐5)₂]²⁺ and an isolated symmetrically linear I₃^‐ anion. The unusual I₇^‐ anion in the heptaiodide can be described as a V‐shaped pentaiodide unit, which is connected with a slightly widened iodine molecule to the rare Z‐form of the heptaiodide ion. In the crystal structure, secondary bonding distances lead to almost planar ten‐membered iodine rings, which are connected by common edges to form staircase‐like bands.     

Über Ethylmethyldiphenylammoniumpolyiodide (EtMePh2N)Ix mit x = 3, 5: Darstellung und strukturelle Charakterisierung eines Triiodids (EtMePh2N)I3 und eines Pentaiodids (EtMePh2N)I5

Studies on Polyhalides. 41. On Ethylmethyldiphenylammoniumpolyiodides (EtMePh₂N)I_x with x = 3, 5: Preparation and Crystal Structures of a Triiodide (EtMePh₂N)I₃ and a Pentaiodide (EtMePh₂N)I₅ So far unknown compounds (EtMePh₂N)I_x with x = 3 and 5 have been prepared and structurally characterized. The triiodide (EtMePh₂N)I₃ crystallizes monoclinically in C2/c with a = 3406.1(3) pm, b = 893.1(1) pm, c = 1222.7(1) pm, β = 99.24(1)° and Z = 8. The crystal structure contains cationic and two kinds of anionic layers alternating along [1 0 0]. One anionic layer is composed of triiodide ions forming the typical and widespread observed herring‐bone pattern. The other one contains zigzag chains (I^– · I₂) along [0 0 1] as a so far not observed structural motif. The pentaiodide (EtMePh₂N)I₅ crystallizes triclinically in P 1 with a = 1020.7(1) pm, b = 1023.1(1) pm, c = 1269.5(1) pm, α = 81.88(1)°, β = 72.66(1)°, γ = 60.65(1)° and Z = 2. The crystal structure is divided into along [0 1 1] alternating puckered cationic and anionic layers. The anions have the common shape of a V, but are here of the rare isolated type. From a topological view two pentaiodide ions are connected to chairlike decagonal rings which are concatenated along [0 1 1].     

Synthese,Charakterisierung und Kristallstrukturen von Tetraiodoferraten(III)

Preparation, Characterization, and Crystal Structures of Tetraiodoferrates(III) The extremely air and moisture sensitive tetraiodoferrates MFeI₄ with M = K, Rb and Cs have been synthesized by reaction of Fe, MI and I₂ at 300°C in closed quartz ampoules. The essentially more stable alkylammonium tetraiodoferrates NR₄FeI₄ with R = H, C₂H₅, n-C₃H₇, n-C₄H₉ and n-C₅H₁₁ can be obtained by reaction of Fe, NR₄I and I₂ in nitromethane. The Raman and UV/Vis-spectra of the black compounds show the existence of tetrahedral [FeI₄]^? ions in the structures. The crystal structure of the monoclinic CsFeI₄ (CsTlI₄ type, spgr P2₁/c; a = 7.281(1) Å; b = 17.960(3) Å; c = 8.248(2) Å; β = 107.35(15)°) is built up by tetrahedral [FeI₄]^? ions and CsI₁₁ polyhedra. The crystal structure of the orthorhombic (n-C₅H₁₁)₄NFeI₄ (spgr Pnna; a = 20.143(4) Å; b = 12.683(3) Å; c = 12.577(3) Å) contains tetrahedral [(n-C₅H₁₁)₄N]⁺ ions and [FeI₄]^? ions, respectively.     

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.     

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.     

Über das Dimethyl(n-propyl)phenylammoniumtriiodid n-PrMe2PhNI3 und die Reihe der Dimethyl(isopropyl)phenylammoniumpolyiodide i-PrMe2PhNIx mit x = 3, 5, 7, 8, 9

Studies of Polyhalides. 35. On the Dimethyl(n-propyl)phenylammoniumtriiodide n-PrMe₂PhNI₃ and on the Series of Dimethyl(isopropyl)phenylammoniumpolyiodides i-PrMe₂PhNI_x with x = 3, 5, 7, 8, and 9 The new compounds n-PrMe₂PhNI₃ and i-PrMe₂PhNI_x with x = 3, 5, 7, 8 and 9 have been prepared by reaction of iodine I₂ with n-PrMe₂PhNI in EtOH and with i-PrMe₂PhNI in MeOH respectively. The crystal structures have been determined by single crystal X-ray diffraction methods. The triiodide n-PrMe₂PhNI₃ has a layerlike structure with alternating anionic and cationic layers. The similar, but not isotypic triiodide i-PrMe₂PhNI₃ may be described as a layerlike packing of asymmetric anions and tetraedral cations, too. The structure of the pentaiodide i-PrMe₂PhNI₅ consists of zig-zag like iodide-diiodine chains with additional iodine molecules attached to the iodide ions in trans position. The pentaiodide part of the heptaiodide ion in i-PrMe₂PhNI₇ forms meanderlike iodide-bis(diiodine) chains also with additional iodine molecules in trans position. The structure of the hexadecaiodide ion I₁₆^2– in the octaiodide i-PrMe₂PhNI₈ contains fourteen-membered rings, which are catenated by iodine molecules and linked to layers with ten- and two types of fourteen membered rings as meshes. The anionic iodine part of the enneaiodide i-PrMe₂PhNI₉ contains fourteen-membered rings, too, which are tied up by two iodine molecules forming in addition ten membered rings which are lined up alternately.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Neue dimere Goldselenolate: Darstellung und strukturelle Charakterisierung von [(n-C4H9)4N]2[AuSSeCC(CN)2]2 und [(n-C4H9)4N]2[AuSe2CC(CN)2]2

New Dimeric Gold Selenolates: Preparation and Characterization of [(n-C₄H₉)₄N]₂[AuSSeC ? C(CN)₂]₂ and [(n-C₄H₉)₄N]₂[AuSe₂C ? C(CN)₂]₂ The preparation and structural characterization of the dimeric Au^I complexes of 1,1-dicyanoethene-2,2-thioseleonlate (i-mnts) and 1,1-dicyanoethene-2,2-diselenolate (i-mns), isolated as Bu₄N salts, are described. They are isotype (monoclinic, space group P2₁/c, Z = 2) with lattice parameters: (Bu₄N)₂[Au(i-mnts)]₂; a = 14.078(3) Å, b = 8.912(3) Å, c = 20.142(4) Å, β = 106.32(5)°; (Bu₄N)₂[Au(i-mns)]₂; a = 13.998(3) Å, b = 9.125(3) Å, c = 20.039(2) Å, β = 105.12(5)°. Ab initio Hartree-Fock calculations based on the experimentally determined structure yield a positive value of the Au? Au bonding order suggesting weak bonding interactions between the d¹⁰ metal centres.     

Metall-Schwefelstickstoff-Verbindungen. 19. Neue Komplexe von CuI mit dem S3N−-Chelatliganden Darstellung und Struktur von [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)] und [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)]

Metal Sulfur-Nitrogen Compounds. 19. Novel Complexes of Cu^I with the S₃N^? Chelate Ligand. Preparation and Structure of [Ph₄As][Cu(S₃N)(CN)], [(Ph₃P)₂N][Cu(S₃N)(S₇N)], and [Ph₄As]₂[(S₃N)Cu(S₂O₃)Cu(S₃N)] In alkaline media S₇NH reacts with Cu salts to yield different products. With Cu(CN) the ion [Cu(S₃N)(CN)]^? is formed, which was isolated as the [Ph₄As]⁺ salt. The crystals are monoclinic, space group P2₁/c, a = 10.499(5), b = 13.418(6), c = 18.032(8) Å, β = 91.84°(3), Z = 4. Besides the known complex ions [Cu(S₃N)₂]^? and [Cu(S₃N)Cl]^? still some more may be obtained when CuCl₂ is reacted with S₇NH: Under special conditions the S₇N ring is partly preserved, and [Cu(S₃N)(S₇N)]^? is formed. Its sparingly soluble [(Ph₃P)₂N]⁺ salt is monoclinic, space group P2₁/n, a = 9.335(6), b = 30.984(11), c = 15.108(8) Å, β = 102.87°(4), Z = 4. Using a longer reaction time a dinuclear complex [(S₃N)Cu(S₂O₃)Cu(S₃N)]^{? ?} results from the reaction of CuCl₂ with S₇NH. The two Cu atoms are bridged by an S atom of the S₂O₃^{? ?} anion. The [Ph₄As]⁺ salt of the dinuclear complex anion is triclinic, space group P1 , a = 11.226(6), b = 12.423(6), c = 19.000(10) Å, β = 76.47°(4), β = 83.98°(4), γ = 84.71°(4), Z = 2. In all these compounds the coordination of Cu^I is trigonal-planar, the S₃N^? chelate group coordinates the Cu in the usual way by two S atoms.     

Untersuchungen an Polyhalogeniden. XVII. Darstellung und Kristallstruktur von Urotropiniumtriiodid,UrHI3

Studies on Polyhalides. 17. Preparation and Crystal Structure of Urotropinium Triiodide, UrHI₃ Urotropinium triiodide C₆H₁₃N₄I₃ is formed by the reaction of equimolar amounts of urotropinium iodide and iodine in ^tBuOH as red-brown cube-like crystals melting at 402 K under decomposition. The compound crystallizes monoclinically in the space group P2₁/c with a = 952.0(3) pm, b = 1 160.2(6) pm, c = 1 149.9(4) pm, β = 92.22(3)° and Z = 4. The till now not described crystal structure (R = 0.027 for 1 860 observed reflexes) contains urotropinium ions UrH⁺ and slightly distorted triiodide ions I₃^?(d(I—I) = 292.3(1), 294.1(1) pm, φ(I—I—I) = 178.27(2)°) which are linked to ion pairs by a rather short contact (d(I …? I) = 389.0(1) pm, φ(I—I …? I) = 149.12(2)°).     

Preparation of new (η5-C5H4CH3)Mn(NO)(PPh3) and (η7-C7H7)Mo(CO)-(PPh3) complexes

The complex (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)I has been prepared by the reaction of NaI with [(η⁵-C₅H₄CH₃)Mn(NO)(CO)(PPh₃)]⁺ and also by the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI followed by PPh₃. This iodide compound reacts with NaCN to yield (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CNC₂H₅)]⁺. Both [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ and [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CO)]⁺ react with NaCN to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂]^?. This anion reacts with Ph₃SnCl to yield cis-(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂SnPh₃ and with [(C₂-H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CNC₂H₅)₂]⁺. The reaction of (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I with AgBF₄ in acetonitrile yields [(η⁵-C₅H₄CH₃)Mn-(NO)(PPh₃)(NCCH₃)]⁺. The complex (η⁵-C₅H₄CH₃)Mn(NO)(CO)I, produced in the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI, is not stable and decomposes to the dimeric complex (η⁵-C₅H₄CH₃)₂Mn₂(NO)₃I for which a reasonable structure is proposed. Similar dimers can be prepared from the other halide salts. The reaction of (η⁷-C₇H₇)Mo(CO)(PPh₃)I with NaCN yields (η⁷-C₇-H₇)Mo(CO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁷-C₇H₇)-Mo(CO)(PPh₃)(CNC₂H₅)]⁺. The interaction of this molybdenum halide complex with AgBF₄ in acetonitrile and pyridine yields [(η⁷-C₇H₇)Mo(CO)(PPh₃)-(NCCH₃)]⁺ and [(η⁷-C₇H₇)Mo(CO)(PPh₃)(NC₅H₅)]⁺, respectively. Both (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I and (η⁷-C₇H₇)Mo(CO)(PPh₃)I are oxidized by NOPF₆ to the respective 17-electron cations in acetonitrile at ?78°C but revert to the neutral halide complex at room temperature. This result is supported by electrochemical data.     

Metall-Schwefelstickstoff-Verbindungen. 20. Reaktionsprodukte von PdCl2 und Pd(CN)2 mit S7NH. Darstellung und Struktur der Komplexe [Ph6P2N][Pd(S3N)(S5)] und X[Pd(S3N)(CN)2] (X = [Me4N]+, [Ph4P]+)

Metal Sulfur Nitrogen Compounds. 20. Reaction Products of PdCl₂ and Pd(CN)₂ with S₇NH. Preparation and Structure of the Complexes [Ph₆P₂N][Pd(S₃N)(S₅)] and X[Pd(S₃N)(CN)₂] X = [Me₄N]⁺, [Ph₄P]⁺ With PdCl₂ and [Ph₆P₂N]OH S₇NH forms the complex salt [Ph₆P₂N][Pd(S₃N)(S₅)], which could be isolated in two modifications (α- and β-form). The α-form is triclinic, a = 9.347(4), b = 14.410(8), c = 15.440(11) Å, α = 76.27°(5), β = 77.06°(4), γ = 76.61α(4), Z = 2, space group P1 . The β-form is orthorhombic, a = 9.333(2), b = 17.659(4), c = 23.950(6) Å, Z = 4. The structure of the metal complex is the same in the two modifications. One S₃N^? and one S₅^2? are coordinate as chelate ligands to Pd. From S₇NH, Pd(CN)₂, and XOH X = [(CH₃)₄N]⁺ and [(C₆H₅)₄P]⁺ the salts X[Pd(S₃N)(CN)₂] were formed. The (CH₃)₄N-salt is isomorphous with the analogous Ni compound described earlier, the (C₆H₅)₄P-salt is triclinic, a = 9.372(4), b = 10.202(5), c = 13.638(6) Å, α = 86.36α(4), β = 85.66°(4), γ = 88.71°(4), Z = 2, space group P1 . One S₃N^? chelate ligand and two CN^? ions are bound to Pd. In all these complexes the coordination of Pd is nearly square planar.     

Strukturen von planaren und tetraedrischen TetrafulminatoMetallkomplexen: [N(C3H7)4]2 [Ni(CNO)4], [N(C3H7)4]2 [Pt(CNO)4] und [N(C3H7)4]2 [Zn(CNO)4]

Pseudohalogeno Metal Compounds. LXXVIII. Structures of Planar and Tetrahedral Tetrafulminato Metal Complexes: [N(C₃H₇)₄]₂ [Ni(CNO)₄], [N(C₃H₇)₄]₂ [Pt(CNO)₄], and [N(C₃H₇)₄]₂ [Zn(CNO)₄] The crystals contain the tetrafulminatometallates of an ideal square planar structure ([Ni(CNO)₄]^2–, [Pt(CNO)₄]^2–) with D_4h symmetry at the nickel and platinum atom and a tetrahedron ([Zn(CNO)₄]^2–) with perfect T_d symmetry at the zinc atom and with linear C≡N–O ligands. The metal carbon bonds (Ni–C: 187 pm, Pt–C: 200 pm, Zn–C: 201 pm) of the metal fulminates are very close to those of the corresponding cyano complexes. In the crystals the anions ([Ni(CNO)₄]^2–, [Pt(CNO)₄]^2–, [Zn(CNO)₄]^2–) are separated by the cations ([N(C₃H₇)₄]⁺) which explains the thermal stability of these compounds.     

Addition des O'Donnell Reagenzes [Ph2C=NCHCO2Me]– an π-koordinierte,ungesättigte Kohlenwasserstoffe in [(C6H7)Fe(CO)3]+, [(C7H9)Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr,Mo) und [(C2H4)Re(CO)5]+. α-Aminosäuren mit metallorganischen Seitenketten

Metal Complexes of Biologically Important Ligands. CXVII [1] Addition of the O'Donnell Reagent [Ph₂C=NCHCO₂Me]^– to Coordinated, Unsaturated Hydrocarbons of [(C₆H₇)Fe(CO)₃]⁺, [C₇H₉Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo), and [(C₂H₄)Re(CO)₅]⁺. α-Amino Acids with Organometallic Side Chains The addition of [Ph₂C=NCHCO₂Me]^– to [(C₆H₇)Fe(CO)₃]⁺, [(C₇H₉)Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo) and [(C₂H₄)Re(CO)₅]⁺ gives derivatives of α-amino acids with organometallic side chains. The structure of [(η⁴-C₆H₇)CH(N=CPh₂)CO₂Me]Fe(CO)₃ was determined by X-ray diffraction. From the adduct of [Ph₂C=NCHCO₂Me]^– and [(C₇H₇)Mo(CO)₃]⁺ the Schiff base of a new unnatural α-amino acid, Ph₂C=NCH(C₇H₇)CO₂Me, was obtained.     

Eine neue und unerwartete Form des Dodecaiodid-Ions I122–: Darstellung und Kristallstruktur des Bis[kalium(dibenzo-18-krone-6)]dodecaiodids [K(C20H24O6)]2I12

Studies of Polyhalides. 32. A New and Unforeseen Shape of the Dodecaiodide Ion I₁₂^2–: Preparation and Crystal Structure of Bis[potassium(dibenzo-18-crown-6)]dodecaiodide [K(C₂₀H₂₄O₆)]₂I₁₂ Particularly iodine rich polyiodides tend to form extended iodine nets by multiply concatenating iodide or triiodide ions through iodine molecules. Therefore the discovery of a not ramified, nearly isolated dodecaiodide ion I₁₂^2– in the new compound [K(C₂₀H₂₄O₆)]₂I₁₂ seems to be unexpected. This ion may be described as an extraordinary long fragment of the triiodide-iodine chain (I₃^– · I₂)_∞.     

Polymere Iodoplumbate – Synthese und Kristallstrukturen von (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF, (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14] · DMF und (Me3N–C2H4–NMe3)2[Pb2I7]I

Polymeric Iodoplumbates – Synthesis and Crystal Structures of (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF, (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF, and (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ) and (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF ( 2 ) have almost the same composition, but completely different structures. Both compounds are formed selectively depending on the reaction and crystallization conditions. In 2 the Pb^II atoms are coordinated either by six bridging I^– ligands in the two-dimensional [Pb₅I₁₄]^4– network or by six DMF ligands in the [Pb(dmf)₆]²⁺ cations. In contrast, (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ) contains non-coordinating I^– anions between the iodoplumbate layers. The iodoplumbate anions in 2 and 3 consist of face and corner sharing PbI₆ octahedra, whereas in 1 PbI₆ and PbI₅(dmf) octahedra share common edges to form a one-dimensional polymeric section of the PbI₂ structure. (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ): Space group P1, a = 920.1(3), b = 1597.2(5), c = 1613.9(4) pm, α = 66.02(2), β = 84.53(2), γ = 85.99(2)°, V = 2156(1) · 10⁶ pm³; (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄]·DMF ( 2 ): Space group P2₁, a = 1201.21(9), b = 3031.1(2), c = 1294.96(9) pm, β = 108.935(7)°, V = 4459.8(5) · 10⁶ pm³; (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ): Space group Pnma, a = 2349.9(2), b = 1623.83(9), c = 980.75(7) pm, V = 3742.4(5) · 10⁶ pm³.