Aryl- und Arin-Komplexe von Übergangsmetallen der sechsten Gruppe Darstellung von [Mo(p-C6H4CH3)6(Li · OC4H10)3] und [W(p-C6H4CH3)4(C6H3CH3)2(Li · OC4H10)4] sowie NMR-spektroskopische Untersuchung des W-Komplexes

Aryl and Aryne Complexes of Group Six Transition Metals. Preparation of [Mo(p-C₆H₄CH₃)₆(Li · OC₄H₁₀)₃] und [W(p-C₆H₄CH₃)₄(C₆H₃CH₃)₂(Li · OC₄H₁₀)₄] and NMR Spectroscopic Investigation of the W Complex Molybdenum(V) chloride reacts with an etheral solution of p-tolyllithium (molar ratio 1:10) to yield a yellow, strongly paramagnetic hexatolylo complex ([MoTol₆(Li · S)₃]¹) (μ_eff = 3.51 B.M.), while from tungsten(V) bromide and p-tolyllithium (molar ratio 1:11) a blackish violet, diamagnetic complex [WTol₄Tn₂(Li · S)₄] is formed, containing two tolylene or tolyne groups for ligands. The ¹H-NMR spectrum points to the Tol-ligands being influenced by the methyl groups of the Tn-ligands.     

The First Organically Templated Layered Uranium(IV) Fluorides: (H3N(CH2)3NH3)U2F10⋅2 H2O, (H3N(CH2)4NH3)U2F10⋅3 H2O,and (H3N(CH2)6NH3)U2F10⋅2 H2O

A new series of layered organically templated uranium(IV ) fluorides has been exclusively synthesized under hydrothermal conditions. The unprecedented materials contain [U₂F₁₀]²⁻ anionic layers that are separated by charge balancing cationic templates and occluded water molecules (see structure depicted). The templates can be fully ion-exchanged for a variety of metals (Na⁺, K⁺, and Co²⁺) at room temperature.     

Crystal structure of [p-C6H4(CH2ImMe)2][PtCl6].

The structure of the title complex consists of a [p-C6H4(CH2ImMe)2]2+ and [PtCl6](2-) pair. The platinum atom is hexacoordinated by six chloride ions in octahedral coordination geometry. The average Pt-Cl bond distance is 2.3199 A. The imidazolium cation and hexachloroplatinate anion are linked via hydrogen bonds, and the crystal packing is governed by the CH...Cl interactions.     

Alkaline Earth Diazapentadienyl Compounds: Structure of [Ba2{(C6H11)NC(Me)CHC(Me)N(C6H11)}3{(SiMe3)2N}]

Three different bonding modes in one molecule! The diazapentadienyl ligands in the title compound 1 adopt η¹,η¹-N,N-chelating plus η⁵-terminal, η¹η¹-N,N chelating plus η⁵-bridging, and novel η¹-N plus η³-1-aza-allyl bonding modes. R=cyclohexyl.     

The σ2π4 Triple Bond between Molybdenum and Tungsten Atoms: Developing the Chemistry of an Inorganic Functional Group

Numerous analogies between organic and inorganic chemistry have emerged in recent years. The most prominent example is the isolobal relationship. Many reactions have shown that metal-metal double and triple bonds exhibit a pattern of reactivity similar to that of alkenes and alkynes. In compounds containing a σ²π⁴ triple bond between molybdenum and tungsten atoms, the M? M bond order can be increased from three to four by reductive elimination or decreased from three to two or one by oxidative addition. Complexes with M?M bonds can be used to prepare clusters or can serve as catalysts. In this review relationships between structure (electronic and stereochemical) and reactivity that are characteristic for modern inorganic chemistry are discussed.     

Four‐ and Five‐Coordinate Gallium Complexes Stabilized by Bidentate 2‐(Dimethylaminomethyl)Pyrrole Ligand: Molecular Structures of Ga[NC4H3(CH2NMe2)‐2]3 and GaMe2[NC4H3(CH2NMe2)‐2]

Treatment of GaCl₃ with one equiv of Li[NC₄H₃(CH₂NMe₂)‐2] (n = 1, 2, 3) in diethyl ether at ?78 °C yields GaCl_3‐n[NC₄H₃(CH₂NMe₂)‐2]_n (n = 1, 1 ; n = 2, 2 ; n = 3, 3 ). Compound 1 reacts with two equiv of RLi to afford GaR₂[NC₄H₃(CH₂NMe₂)‐2] ( 4a, R=Me; 4b, R=Bu ) via transmetallation. Reacting 2 with one equiv of RLi in diethyl ether, 3 and 4 are formed via ligand redistribution. Variable temperature ¹H NMR spectroscopic experiments reveal that the five‐coordinate gallium compound 3 is fluxional and results in a coalescence temperature at 5 °C, at which ΔG^≠ is calculated at ca. 10.4 Kcal/mole. All the new compounds have been characterized by ¹H and ¹³C NMR spectroscopy and the structures of compounds 3 and 4a have also been determined by X‐ray crystallography.     

Zur Umsetzung von Kupfer(I)‐ und Kupfer(II)‐Salzen mit P(C6H4CH2NMe2‐2)3 ‐ die Festkörperstrukturen von {[P(C6H4CH2NMe2‐2)3]CuOClO3}ClO4, {[P(C6H4CH2NMe2‐2)3]Cu}ClO4, [P(C6H4CH2NMe2‐2)3]CuONO2 und [P(C6H4CH2NMe2‐2)2(C6H4CH2NMe2H+NO3‐‐2)]CuONO2

Reaction Behaviour of Copper(I) and Copper(II) Salts Towards P(C₆H₄CH₂NMe₂‐2)₃ ‐ the Solid‐State Structures of {[P(C₆H₄CH₂NMe₂‐2)₃]CuOClO₃}ClO₄, {[P(C₆H₄CH₂NMe₂‐2)₃]Cu}ClO₄, [P(C₆H₄CH₂NMe₂‐2)₃]CuONO₂ and [P(C₆H₄CH₂NMe₂‐2)₂(C₆H₄CH₂NMe₂H⁺NO₃^‐‐2)]CuONO₂ The reaction behaviour of P(C₆H₄CH₂NMe₂‐2)₃ ( 1 ) towards different copper(II) and copper(I) salts of the type CuX₂ ( 2a : X = BF₄, 2b : X = PF₆, 2c : X = ClO₄, 2d : X = NO₃, 2e : X = Cl, 2f : X = Br, 13 : X = O₂CMe) and CuX ( 5a : X = ClO₄, 5b : X = NO₃, 5c : X = Cl, 5d : X = Br) is discussed. Depending on X, the transition metal complexes [P(C₆H₄CH₂NMe₂‐2)₃Cu]X₂ ( 3a : X = BF₄, 3b : X = PF₆), {[P(C₆H₄CH₂NMe₂‐2)₃]CuX}X ( 4 : X = ClO₄, 11a : X = Cl, 11b : X = Br, 14 : X = O₂CMe), {[P(C₆H₄CH₂NMe₂‐2)₃]Cu}ClO₄ ( 6 ), [P(C₆H₄CH₂NMe₂‐2)₃]CuX ( 7a : X = Cl, 7b : X = Br, 10 : X = ONO₂), [P(C₆H₄CH₂NMe₂‐2)₂(C₆H₄CH₂NMe₂H⁺NO₃^‐‐2)]CuONO₂ ( 9 ) and [P(C₆H₄CH₂NMe₂‐2)₃]CuCl}CuCl₂ ( 12 ) are accessible. While in 3a , 3b and 6 the phosphane 1 preferentially acts as tetrapodale ligand, in all other species only the phosphorus atom and two of the three C₆H₄CH₂NMe₂ side‐arms are datively‐bound to the appropriate copper ion. In solution a dynamic behaviour of the latter species is observed. Due to the coordination ability of X in 3a , 3b and 6 non‐coordinating anions X^‐ are present. However, in 4 one of the two perchlorate ions forms a dative oxygen‐copper bond and the second perchlorate ion acts as counter ion to {[P(C₆H₄CH₂NMe₂‐2)₃]CuOClO₃}⁺. In 7 , 9 and 10 the fragments X (X = Cl, Br, ONO₂) form a σ‐bond with the copper(I) ion. The acetate moiety in 14 acts as chelating ligand as it could be shown by IR‐spectroscopic studies. All newly synthesised cationic and neutral copper(I) and copper(II) complexes are representing stable species. Redox processes are involved in the formation of 9 and 12 by reacting 1 with 2 . The solid‐state structures of 4 , 6 , 9 and 10 are reported. In the latter complexes the copper(II) ( 4 ) or copper(I) ion ( 6 , 9 , 10 ) possesses the coordination number 4. This is achieved by the formation of a phosphorus‐ and two nitrogen‐copper‐ ( 4 , 9 , 10 ) or three ( 6 ) nitrogen‐copper dative bonds and a coordinating ( 4 ) or σ‐binding ( 9 , 10 ) ligand X. In 6 all three nitrogen and the phosphorus atoms are coordinatively bound to copper, while X acts as non‐coordinating counter‐ion. Based on this, the respective copper ion occupies a distorted tetrahedral coordination sphere. While in 4 and 10 a free, neutral Me₂NCH₂ side‐arm is present, which rapidly exchanges in solution with the coordinatively‐bound Me₂NCH₂ fragments, this unit is protonated in 10 . NO₃^‐ acts as counter ion to the CH₂NMe₂H⁺ moiety. In all structural characterized complexes 6‐membered boat‐like CuPNC₃ cycles are present.     

Schwermetall-π-Komplexe. IX. Die Kettenpolymere [(1,2- (CH3)2C6H4BiCl3)2], [(1,3) (CH3)2C6H4BiCl3)2] und [(1,4- (CH3)2C6H4BiCl3)2]

Heavy Metal π-Complexes. IX. The Chain Polymers [(1,2- (CH₃)₂C₆H₄BiCl₃)₂], [(1,3- (CH₃)₂C₆H₄BiCl₃)₂] and [(1,4- (CH₃)₂C₆H₄BiCl₃)₂] In the crystal structures of the three solid state complexes (C₆H₄(CH₃)₂BiCl₃ (C₆H₄(CH₃)₂ = o-xylene: 1 , m-xylene: 2 , p-xylene: 3 ) quasi-dimeric units of almost undistorted, arene coordinated BiCl₃ fragments can be found that are further associated via additional Bi? Cl contacts to form one-dimensional polymeric chains. Whereas the chains of 2 and 3 are constituted by Bi₂Cl₂ four-membered rings only, further Cl-bridging in 1 leads to additional trigonal-bipyramidal arrangements with Bi atoms exhibiting coordination numbers of 3 + 3 + 1 and 3 + 2 + 1, respectively (prim. + sec. Cl contacts + arene). The arene-metal bonding is characterized by Bi-arene distances in the range from 297 – 306 pm, including ring slippages of 24 –41 pm and 73 pm with the Bi atoms being six and seven coordinated, respectively. The direction of this slipping with respect to the arene's methylation sites cannot be understood in terms of electronic influences but is shown to be caused by steric demands. The values IP₁ of the arenes prove to determine the colours of the complexes.     

Melemium Hydrogensulfate H3C6N7(NH2)3(HSO4)3 – the First Triple Protonation of Melem

We synthesized melemium hydrogensulfate H₃C₆N₇(NH₂)₃(HSO₄)₃ by reaction of melem with 70 % sulfuric acid. The crystal structure was elucidated by single‐crystal XRD (P2₁/n (no. 14), Z = 4, a = 10.277(2), b = 14.921(3), c = 11.771(2) Å, β = 99.24(3)°, V = 1781.5(6) Å³). H₃C₆N₇(NH₂)₃(HSO₄)₃ is the first compound displaying a triple protonation of melem., In this contribution an overview of accessible melemium sulfates depending on the concentration of sulfuric acid is given. Two additional melemium sulfates were identified this way.     

Darstellung und NMR-spektroskopische Untersuchung eines hexakoordinierten p-Tolylo-tantal(V)-Komplexes: [(p-CH3C6H4)5 Ta(p-CH3C6H4)Li · O(C2H5)2]

Preparation and N.M.R.-spectroscopie Investigation of a Hexacoordinated p-Tolylotantalum(V) Complex: [(p-CH₃C₆H₄)₅Ta(p-CH₃C₆H₄)Li · O(C₂H₅)₂] Reaction of tantalum(V) bromide with an etheral solution of p-tolyllithium in the molar ratio 1:5 leads to precipitation of a yellow complex of the brutto formula LiTaTol₆ · Ae[Tol = p-CH₃C₆H₄^?; Ae = (C₂H₅)₂O]. The ¹H and ¹³C n.m.r. spectra are discussed.