The interaction of group III metal alkyls with crown ethers. The synthesis and structure of [Ga(CH3)3]2[dibenzo18-crown-6] and [Al(CH3)3]2[dicyclohexano-18-crown-6]

[Ga(CH₃)₃]₂[dibenzo-18-crown-6] and [Al(CH₃)₃]₂[dicyclohexyl-18-crown-6] were prepared by the reaction of Ga(CH₃)₃ or Al(CH₃)₃ with the appropriate crown ether in toluene. After filtering and cooling, both products were obtained as colorless, air-sensitive, rectangular crystals. The structures of both compounds were determined from single crystal X-ray diffraction data collected on a CAD-4 diffractomer. [Ga(CH₃)₃]₂[dibenzo-18-crown-6] belongs to the monoclinic space group P2₁/c with unit cell parameters a 11.460(5), b 18.000(7), c 7.495(4) Å, β 105.65(4)°, and ϱ(calc) 1.32 g cm⁻³ for Z  2. Least-squares refinement gave a final R value of 0.061 for 1179 independent observed reflections. The molecule resides on a crystallographic center of inversion. The Ga-O distance of 2.198(8) Å is among the longest yet observed. In order to accommodate the two trialkygallium units, the crown ether is forced to adopt a chair configuration. [Al(CH₃)₃]₂[dicyclohexano-18-crown-6] crystallizes in the space group P2₁/a with cell parameters a 16.423(7), b 9.812(5), c 20.935(8) Å, β 107.41(5)°, and ϱ(calc) 1.07 g cm⁻³ for Z  4. Least-squares refinement gave a final R value of 0.079. The flexibility of the crown ether in this case allows the bonded oxygen atoms to be positioned on the outside of the crown, with all six oxygen atoms in a near-planar arrangement.     

Die Reaktion des [(Me3Si)2CH]2Al?CH2?Al [CH(SiMe3)2]2 mit Neopentyllithium: Bildung des {[(Me3Si)2CH]2Al?CH2?Al [CH(SiMe3)2]2CH2CMe3}⊖ [Li(TMEDA)2]⊕

Reaction of [(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂ with Neopentyllithium: Formation of {[(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂CH₂CMe₃} ? [Li(TMEDA)₂]⊕ The recently synthesized methylene bridged dialuminium compound [(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂ reacts with neopentyl lithium in the presence of TMEDA to give the stable {[(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂CH₂ · CMe₃}? [Li(TMEDA)₂]⊕ decomposing at 115°C. The aluminium atoms therein are not additionally bridged, but the new substituent is occupying a terminal position as detected by crystal structure determination. A compound is formed containing a saturated, fourfold coordinated neighbouring a formally unsaturated, threefold coordinated aluminium atom. Due to high sterical restrictions the Al? C bonds are lengthened up to 209.0(3) pm at the alanate site and the Al? C? Al angle in the methylene bridge is extraordinarily enlarged to 144.4(2)°.     

Zur solvensfreien Darstellung von Tetramethylammoniumsalzen: Synthese und Charakterisierung von [N(CH3)4]2[C2O4], [N(CH3)4][CO3(CH3)], [N(CH3)4][NO2], [N(CH3)4][CO2H] und [N(CH3)4][O2C(CH2)2CO2(CH3)]

Solvent-free Synthesis of Tetramethylammonium Salts: Synthesis and Characterization of [N(CH₃)₄]₂[C₂O₄], [N(CH₃)₄][CO₃CH₃], [N(CH₃)₄][NO₂], [N(CH₃)₄][CO₂H], and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] A general procedure to synthesize tetramethylammonium salts is presented. Several tetramethylammonium salts were prepared in a crystalline state by solvent-free reaction of trimethylamine and different methyl compounds at mild conditions: [N(CH₃)₄]₂[C₂O₄] (cubic; a = 1 114.8(3) pm), [N(CH₃)₄][CO₃CH₃] (P2₁/n; a = 813.64(3), b = 953.36(3), c = 1 131.3(4) pm, β = 90.03(1)°), [N(CH₃)₄][NO₂] (Pmmn; a = 821.2(4), b = 746.5(3), c = 551.5(2) pm), [N(CH₃)₄][CO₂H] (Pmmn; a = 792.8(7), b = 791.7(3), c = 563.3(4) pm) and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] (P2₁; a = 731.1(2), b = 826.4(3), c = 1 025.2(3) pm, β = 110.1(1)°). The tetramethylammonium salts were characterized by IR-spectroscopy and X-ray diffraction. The crystal structures of the methylcarbonate and the nitrite are described.     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

Schwingungsspektrum und Kraftkonstanten des Tetrakis-trimethylsilyl-hydrazin,[(CH3)3Si]2N-N[Si(CH3)3]2

The vibrational spectra (IR and RAMAN ) have been taken for tetrakis-trimethylsilyl-hydrazine. A complete assignment of all observed bands is given. The silicium-nitrogen vibrations are interpreted in terms of a D_2d configuration. Force constants of the GVFF are computed. The valency force constant of the nitrogen-nitrogen bond is comparable to that of N₂H. This proves the interaction of the silicium atoms with the free electron pairs of the two nitrogen atoms.     

A Tri-Coordinate-Magnesium Silylamide Complex: {[(CH3)3Si]2N}2MgO(CH2CH2)2OMg{N[Si(CH3)3]2}2

The reaction of diethylmagnesium dioxane adduct solution with 1,1,1,3,3,3-hexamethyldisilazan ((CH₃)₃SiNHSi(CH₃)₃) gives {[(CH₃)₃Si]₂N}₂MgO(CH₂CH₂)₂OMg{N[Si(CH₃)₃]₂}₂ (1); this alkoxomagnesium silylamide in the solid state contains unprecedented three-coordinate magnesium and oxygen atoms.     

Bis(pyrazolylethyl)thioether ligation to zinc and cadmium: structural characterization of [S(CH2CH2pzMe2)2]ZnCl2, [S(CH2CH2pzMe2)2]CdI2 and [S(CH2CH2pzMe2)2]Cd(NO3)2

Structural characterization of [S(CH₂CH₂pz^Me₂)₂]ZnCl₂ by X-ray diffraction demonstrates that the potentially tridentate [NNS] donor ligand S(CH₂CH₂pz^Me₂)₂ does not coordinate via sulfur, but only binds through the pyrazolyl groups. Furthermore, the ligand does not chelate, but preferentially bridges two zinc centers, thereby resulting in a polymeric, helical, structure. In contrast to the zinc system, the thioether functionality does bind to cadmium in related derivatives, [S(CH₂CH₂pz^Me₂)₂]CdI₂ and [S(CH₂CH₂pz^Me₂)₂]Cd(NO₃)₂.     

双核有机锡(Ⅳ)配合物[Ph_3Sn(CH_3OH)O_2CC_6H_4CO_2(CH_3OH)-SnPh_3]·2CH_3OH和[Ph_3SnS_2CN(CH_2CH_2)_2NCS_2SnPh_3]·2CH_3OH的合成、表征和晶体结构

利用三苯基氯化锡和对苯二甲酸二钠、哌嗪荒酸二钠在甲醇中反应 ,合成了双核有机锡 (Ⅳ )配合物 [Ph3 Sn (CH3 OH)O2 CC6H4 CO2 (CH3 OH)SnPh3 ]·2CH3 OH (1)和 [Ph3 SnS2 CN(CH2 CH2 ) 2 NCS2 SnPh3 ]·2CH3 OH (2 ) .通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征 .用X射线单晶衍射测定了这两个化合物的晶体结构 .化合物 1为单斜晶系 ,空间群P2 1/n ,a =1.5 199(5 )nm ,b =0 .90 0 0 (3)nm ,c =1.82 0 6 (6 )nm ,β =113.970 (5 )° ,Z =2 ,V =2 .2 75 5(13)nm3 ,Dc=1.413g/cm3 ,μ =1.146mm-1,F(0 0 0 ) =980 ,R1=0 .0 35 3,wR2 =0 .0 6 0 6 .化合物 2为单斜晶系 ,空间群P2 1/c,a =1.5 0 6 6 (5 )nm ,b =1.0 875 (4 )nm ,c =1.35 42 (5 )nm ,β =91.6 14(5 )°,Z =2 ,V =2 .2 178(14)nm3 ,Dc=1.498g/cm3 ,μ =1.35 1mm-1,F(0 0 0 ) =10 0 8,R1=0 .0 40 1,wR2 =0 .1148.在 1和 2的晶体中 ,锡原子呈五配位畸变三角双锥构型 .配合物 1由未配位的甲醇分子通过氢键作用形成二维网状结构     

Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

A novel chain-like molybdenum phosphate: hydrothermal synthesis,crystal structure and characterization of [NH3(CH2CH2)2NH3]3[NH3(CH2CH2)2NH2]-Na5[Mo6O12(OH)3(PO4)(HPO4)3]2·4H2O

A novel organic/inorganic hybrid molybdenum phosphate, [NH₃(CH₂CH₂)₂NH₃]₃[NH₃(CH₂CH₂)₂NH₂]Na₅-[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂·4H₂O (1), involving molybdenum presented in V oxidation, has been hydrothermally prepared and characterized by elemental analysis, i.r., u.v.–vis., x.p.s., t.g. and single crystal X-ray diffraction. The structure of the title compound (1) may be considered to consist of two [Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃] units bonded together with NaO₆ octahedra, forming dimers. Further, these dimers connect with each other through four Na⁺ cations as bridges, giving rise to novel one-dimensional chain-like skeleton. Piperazines exist among inorganic chains acting as charge balancing cations.     

Synthesis,Crystal Structure,and Spectroscopic Characterization of the Borazine Derivatives [B{CH2(SiCl3)}NH]3 and [B{CH2(SiCl2CH3)}NH]3

The borazine derivatives B, B′, B″‐tris[(trichlorosilyl)methyl]borazine [B{CH₂(SiCl₃)}NH]₃ ( 1 ), and B, B′, B″‐tris[{dichloro(methyl)silyl}methyl]borazine [B{CH₂(SiCl₂CH₃)}NH]₃ ( 2 ) were prepared by reacting (Cl₃Si)CH₂(BCl₂) ( 3 ) and [Cl₂(CH₃)Si]CH₂(BCl₂) ( 4 ) with hexamethyldisilazane (hmds), respectively. Both compounds, 1 and 2 crystallize in space group R3c with a = 1712.53(4), c = 1230.33(4) pm, Z = 6, R₁ = 0.030, and a = 1713.8(2), c = 1258.7(2) pm, Z = 6, R₁ = 0.034, respectively. According to the single crystal X‐ray diffraction analyses, the title compounds show a planar B₃N₃ six‐membered ring with B—N distances of 142.3(3) pm (point symmetry C₃) and synfacial oriented substituents. The borazine derivatives have also been characterized by NMR and IR spectroscopy as well as by MS spectrometry.     

Syntheses and structural study of trinuclear iron acetates [Fe3O(CH3COO)6(H2O)3]Cl· 6H2O and [Fe3O(CH3COO)6(H2O)3] [FeCl4]· 2CH3COOH

The structure of two trinuclear iron acetates [Fe₃O(CH₃COO)₆(H₂O)₃]Cl· 6H₂O (I) and [Fe₃O(CH₃COO)₆(H_2O)₃][FeCl₄] · 2CH₃COOH (II) was determined by X-ray diffraction analysis. Crystals I and II are ionic and belong to the orthorhombic system with parameters a = 13.704(3), b = 23.332(5), c = 9.167(2) Å, R = 0.0355, space goup P2₁2₁2 for I and a = 10.145(4), b = 15.323(6), c = 22.999(8) Å, R = 0.0752, space group Pbc2₁ for II. The complex cation [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ has a μ₃-O-bridged structure typical for trinuclear iron (III) compounds. As shown by Mössbauer spectroscopy, the iron(III) ions are in the high-spin state. In trinuclear cations, antiferromagnetic exchange interaction takes place between the Fe(III) ions with the exchange parameter J = -26.69 cm^?1 for II (Heisenberg-Dirac-Van Vleck model for D_3h, symmetry).     

Die Reaktion des [(Me3Si)2CH]2Al?CH2?Al [CH(SiMe3)2]2 mit LiCH(PMe2)2; Bildung eines fünfgliedrigen Al2C2P-Heterozyklus

The Reaction of [(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂ with LiCH(PMe₂)₂; Formation of a Five-membered Al₂C₂P Heterocycle The recently synthesized methylene bridged dialuminium compound [(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂ 3 reacts with one equivalent of LiCH(PMe₂)₂ in the presence of TMEDA to give an adduct with one aluminium atom coordinated by the carbanionic carbon atom and the second one coordinated by one phosphorus atom. A five-membered heterocycle 5 is formed, which was characterized by a crystal structure determination showing a strongly bent ring with the phosphorus atom located above the plane of the four remaining atoms (Al₂C₂). 5 is unstable in ethereal solution decomposing under ether cleavage to the educt 3 and the diphosphinomethane derivative CH₂(PMe₂)₂.