Thermogravimetric,Cyclovoltammetric, and Mössbauer Spectroscopic Investigations on Heterobimetallic Organo Derivatives of Silicon and Germanium with the 2‐(Dimethylaminomethyl)ferrocenyl Ligand (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)], FcN

The thermic decomposition of the cyclotetrametaloxanetetrols [(FcN)₄M₄O₄(OH)₄] (M= Si( 1 ), Ge( 2 )) as well as the cyclohexagermoxanediol [(FcN)₆Ge₆O₈(OH)₂] ( 3 ) takes place in three defined steps. At the monomer silandiol [(FcN)₂Si(OH)₂] ( 4 ) only two such steps are observed. The cyclovoltammetric oxidation of the metaloxanes 1 ‐ 2 occurs in two two‐electron steps and following two one‐electron transitions. The oxidation of 3 occurs in a four‐electron process and a following two‐electron transition. Silandiol 4 is oxidized via two one‐electron transitions. The oxidation of the educt [FcNGeCl₃] ( 5 ) occurs in a one‐electron step. Temperature depending ⁵⁷Fe‐Mössbauer‐measurements confirm as well intervalent electron transitions in 1 ‐ 5 as the chelate stucture in 5 .     

[Ge4O6Te4]4—, an Adamantanoid Oxotellurido Germanate(IV) with a Central Ge4O6 Core

[Mn(en)₃]₂[Ge₄O₆Te₄]·1.5en ( 1 ) and (enH)₃[Mn(en)₃]₃[Ge₄O₆Te₄]₂I·4.7en ( 2 ) may be prepared at 150 °C by solvothermal reaction of elemental Ge and Te with Mn(OOCCH₃)₂ ·4H₂O in the presence of [CH₃)₄N]I as a mineralizer in respectively superheated ethylenediamine (en) or an en/CH₃OH (3:2) mixture. Both contain the novel [Ge₄O₆Te₄]^4— anion with a central adamantanoid Ge₄O₆ core and four terminal Te atoms and represent the first examples of such a mixed [M₄E₆E₄′]^4— anion (M = Si‐Sn; E = O‐Te). As a result of their increased polarity, the Ge‐Te bonds of 2 are markedly shorter (2.438 — 2.462Å) than those previously reported for telluridogermanates(IV).     

Cluster self-organization of germanate systems: Suprapolyhedral precursor clusters and self-assembly of K2Nd4Ge4O13(OH)4, K2YbGe4O10(OH), K2Sc2Ge2O7(OH)2, and KScGe2O6(PYR)

Geometric and topological analysis of all known types of K,TR germanates (TR = La-Lu, Y, Sc, In) is carried out with the use of computer techniques (the TOPOS 4.0 program package). Framework structures are represented as three-dimensional (3D) K,TR,Ge networks (graphs) with oxygen atoms removed. The following crystal-forming 2D TR,Ge networks are determined: for K₂Nd₄Ge₄O₁₃(OH)₄, this is TR 4 3 3 4 3 3 + T 4 3 4 3; for K₂YbGe₄O₁₀(OH), this is TR 6 6 3 6 + T 1 6 8 6 + T 2 3 6 8; for K₂Sc₂Ge₂O₇(OH)₂, this is TR 6 4 6 4 + T 6 4 6; and for KScGe₂O₆, TR 6 6 3 6 3 4 + T 1 6 3 6 + T 2 6 4 3. The full 3D reconstruction of the self-assembly mechanism of crystal structures is performed as follows: precursor cluster—primary chain—microlayer-microframework (supraprecursor). In K₂Nd₄Ge₄O₁₃(OH)₄, K₂Sc₂Ge₂O₇(OH)₂, and KScGe₂O₆, an invariant type of cyclic six-polyhedral precursor cluster is identified; this precursor clusters is built of TR octahedra, which are stabilized by atoms K. For K₂Nd₄Ge₄O₁₃(OH)₄, the type of cyclic four-polyhedral precursor cluster of tetrahedron-linked TR octatopes is identified. The cluster coordination number in a layer is six (the maximum possible value) only for anhydrous germanate KScGe₂O₆ (an analogue of pyroxene, PYR); in the other OH-containing germanates, this number is four. The mechanism of formation of Ge radicals in the form of groups Ge₂O₇ and Ge₄O₁₃, a chain GeO₃, and a tubular assembly of linked cyclic groups Ge₈O₂₀ is considered.     

Darstellung,Eigenschaften und Molekülstrukturen von Heterobimetallorganika des vierwertigen Germaniums mit dem 2‐(Dimethylaminomethyl)ferrocenyl‐Liganden FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)‐2]

Hydrolysereak‐Syntheses, Properties and Molecular Structures of the Heterobimetalorganics of the four‐valued Germanium with the 2‐(Dimethylaminomethyl)ferrocenyl Ligand FcN (η⁵‐C₅H₅)Fe[η⁵‐C₅H₃(CH₂NMe₂)‐2] The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, FcNLi, reacts with germanium(IV) chloride, GeCl₄, under the formation of heterobimetallic germanium(IV) organyls (FcN)_nGeCl_4‐n (n = 2 ( 1 ), 3 ( 2 )). The heterobimetallic organogermanol (FcN)₃GeOH ( 3 ) is formed at hydrolysis of 2 . A detailed characterization of the defined compounds 1 — 3 was carried out by single crystal X‐ray analyses, NMR‐ and mass‐spectrometry.     

Synthesen und Charakteristika von Heterobimetallorganika des Siliciums mit dem 2‐(Dimethylaminomethyl)ferrocenyl‐Liganden FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)]—

Syntheses and characteristics of the heterobimetalorganics of the silicon with the 2‐(dimethylaminomethyl)ferrocenyl ligand FcN (η⁵‐C₅H₅)Fe[η⁵‐C₅H₃(CH₂NMe₂)]^— The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, LiFcN, reacts with silicon(IV)‐chlorid, SiCl₄, under the formation of heterobimetallic silicon(IV) organyl [(FcN)₃SiCl] ( 1 ). The heterobimetallic organosilanol [(FcN)₃SiOH] ( 2 ) is formed at hydrolysis of 1 . A detailed characterization of the defined compounds 1 and 2 was carried out by NMR‐ rsp. mass‐spectrometry and by crystal X‐ray analysis of 2 .     

Syntheses,structures, and magnetism of {V15M6O42(OH)6(Cl)} (M = Si,Ge)

Two [V₁₅M₆(OH)₆O₄₂(Cl)]^7? (M = Si for 1, Ge for 2) cluster anions with protonated amines as counterions have been synthesized under hydrothermal conditions and characterized by FT-IR, energy dispersive spectroscopy, XPS, powder X-ray diffraction, thermogravimetric analysis (TGA), elemental analysis, and single-crystal X-ray analyses. Both compounds consist of {V₁₅M₆O₄₂(OH)₆(Cl)} (M = Si for 1, Ge for 2), which are derived from {V₁₈O₄₂} by substitution of three {VO₅} square pyramids with three {Si₂O₅(OH)₂/Ge₂O₅(OH)₂} units. It represents the first example of cage-like polyoxovanadates (POVs) containing three (Si/Ge)₂O₅(OH)₂ units. There are extensive hydrogen bonding interactions between POVs and organoamines in 1 and 2. Compound 1 presents a close-packed layer aggregate, while 2 exhibits the packing of six-membered rings with a 1-D channel. Magnetism measurements demonstrate the presence of strong antiferromagnetic interaction between V^IV centers in 1.     

Ein anionischer Oxohydroxo‐Komplex mit Bismut(III): Na6[Bi2O2(OH)6](OH)2 · 4H2O

An Anionic Oxohydroxo Complex with Bismuth(III): Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O Colourless, plate‐like, air sensitive crystals of Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O are obtained by reaction of Bi₂O₃ or Bi(NO₃)₃ · 5H₂O in conc. NaOH (58 wt %) at 200 °C followed by slow cooling to room temperature. The crystal structure (triclinic, P 1¯, a = 684.0(2), b = 759.8(2), c = 822.7(2) pm, α = 92.45(3)°, ß = 90.40(3)°, γ = 115.60(2)°, Z = 1, R1, wR2 (all data), 0, 042, 0, 076) contains dimeric, anionic complexes [Bi₂O₂(OH)₆]^4— with bismuth in an ψ¹‐octahedral coordination of two oxo‐ and three hydroxo‐ligands. The thermal decomposition was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In the final of three steps the decomposition product is Na₃BiO₃.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

The First Examples of Selenidogermanate Salts with Lanthanide Complex Counter Cations: Solvothermal Syntheses and Characterizations of [{Ln(en)3}2(μ‐OH)2]Ge2Se6 (Ln = Eu,Ho) and [{Ho(dien)2}2(μ‐OH)2]Ge2Se6

The lanthanide selenidogermanates [{Eu(en)₃}₂(μ‐OH)₂]Ge₂Se₆ ( 1 ), [{Ho(en)₃}₂(μ‐OH)₂]Ge₂Se₆ ( 2 ), and [{Ho(dien)₂}₂(μ‐OH)₂]Ge₂Se₆ ( 3 ) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally prepared by the reactions of Eu₂O₃ (or Ho₂O₃), germanium, and selenium in en and dien solvents respectively. Compounds 1 – 3 are composed of selenidogermanate [Ge₂Se₆]^4– anion and dinuclear lanthanide complex cation [{Ln(en)₃}₂(μ‐OH)₂]⁴⁺ (Ln = Eu, Ho) or [{Ho(dien)₂}₂(μ‐OH)₂]⁴⁺. The [Ge₂Se₆]^4– anion is composed of two GeSe₄ tetrahedra sharing a common edge. The dinuclear lanthanide complex cations are built up from two [Ln(en)₃]³⁺ or [Ho(dien)₂]³⁺ ions joined by two μ‐OH bridges. All lanthanide(III) ions are in eight‐coordinate environments forming distorted bicapped trigonal prisms. In 1 – 3 , three‐dimensional supramolecular networks of the anions and cations are formed by N–H ··· Se and N–H ··· O hydrogen bonds. To the best of our knowledge, 1 – 3 are the first examples of selenidogermanate salts with lanthanide complex counter cations.     

Reactivity of [(Ph2Si)2O3]4[Al(OH)]4 and [(Ph2Si)2O3]4[Al(OLi)]4 towards NaOEt and LiOH. Synthesis of New Twelve‐membered Alumopolysiloxane Rings

The reaction between [(Ph₂Si)₂O₃]₄[Al(OH)]₄ ( 1 ) or [(Ph₂Si)₂O₃]₄[Al(OLi)]₄ ( 2 ) with sodium ethoxide, or lithium hydroxide in presence of CuI·H₂O leads to the formation of new alumopolysiloxane compounds. Indeed, transformations of 1 under the partial incorporation of the reactants are found giving rise to new heteroleptic inorganic macrocycles. The molecular structure of [(Ph₂Si)₂O₃]₄[Al(ONa)]₂[Al(OH)(NaOEt)]₂·2Et₂O ( 3 ) and [(Ph₂Si)₂O₃]₄[Al(OLi)]₂[Al(OH)(LiOH)]₂·2Et₂O·2THF ( 4 ) have been determined by single‐X‐ray diffraction analysis. Both alumosiloxanes 3 and 4 are constituted by a twelve‐membered ring.     

Cluster self-organization of germanate systems: Suprapolyhedral precursor nanoclusters and self-assembly of CAN-Na8(Al6Ge6O24)Ge(OH)6(H2O)2 and CAN-Cs2Na6(Al6Ge6O24)Ge(OH)6) zeolite crystal structures re]20100419

Geometrical and topological analysis of zeolite crystal structures having a tetrahedral framework of the cancrinite (CAN) type, namely, (CAN) Na₈(Al₆Ge₆O₂₄)Ge(OH)₆(H₂O)₂ (acentric space group P6₃, hP64, Na-CAN) and Cs₂Na₆(Al₆Ge₆O₂₄)Ge(OH)₆ (P6₃, hP52, CsNa-CAN), is carried out with the use of computer techniques (the TOPOS 4.0 program package). An AT ₆ hexapolyhedral precursor nanocluster centered with a template cation A (Na, Cs) is identified. The topological type of a two-dimensional (2D) crystalforming T-net 4.6.12, which corresponds to a uninodal semiregular Shubnikov net, is recognized. The full 3D reconstruction of crystal structure self-assembly is performed as follows: precursor nanocluster → primary chain → microlayer → microframework → … framework. The symmetry of an AT6 precursor nanocluster is described by point group 3; the symmetry axis passes through the center of the nanocluster and cation A. The coordination number (CN) of a precursor nanocluster, which characterizes the nanocluster stacking in the macrostructure, is six. In both structures, six Na atoms and a Ge(OH)₆ polyhedral species are spacers filling the voids between AT ₆ precursor nanoclusters. The Ge(OH)₆ polyhedral species is characterized by four and two orientationally allowed positions in Na-CAN and CsNa-CAN, respectively. The minimal number of suprapolyhedral AT ₆ precursor nanoclusters required for the 3D microframework to form is 16; that is, 96 tetrahedra are involved in microframework self-assembly.     

Die Kristallstruktur von Ag2Ge2O5: Eine neuartige Gerüststruktur von Ge2O52−

Crystal Structure of Ag₂Ge₂O₅: A New Ge₂O₅^2? Network Structure Ag₂Ge₂O₅ was prepared from the binary oxides at high O₂ pressures. Single crystal X-ray diffraction work indicated monoclinic symmetry (P2₁/c; a = 1101.3(2); b = 1006.3(1); c = 1221.9(3) pm; ß = 94.6(1)°). The structure was determined by direct methods (3372 independent structure factors) and refined to a conventional R value of 0.084. A new Ge₂O₅^2? network structure was found with germanium coordinated octahedrally (­d(Ge—O) = 188,7 pm) and tetrahedrally (­d(Ge—O) = 175,9 pm), in equal proportions, by oxygen. The polyhedra share vertices and edges, thus forming a three dimensional channel system, which is occupied by Ag⁺ ions. The shortest Ag—Ag distance of 284 pm, like the pale yellow colour of the compound, indicates Ag⁺—Ag⁺ interaction.     

(Ph4P)2[Be3(μ‐OH)3(H2O)6]Cl5: Kristallstruktur und DFT‐Rechnungen

Bis(tetraphenylphosphonium)‐tris(μ‐hydroxo)hexaaquatriberylliumpentachloride, (Ph₄P)₂[Be₃(μ‐OH)₃(H₂O)₆]Cl₅ ( 1 ), was surprisingly obtained by reaction of (Ph₄P)N₃ · n H₂O with BeCl₂ in dichloromethane suspension and subsequent crystallization from acetonitrile to give single crystals of composition 1· 5.25CH₃CN. According to the crystal structure determination space group P , Z = 2, lattice dimensions at 100 K: a = 1354.8(2), b = 1708.7(2), c = 1753.2(2) pm, α = 114.28(1)°, β = 94.80(1)°, γ = 104.51(1)°, R₁ = 0.0586] the [Be₃(μ‐OH)₃(H₂O)₆]³⁺ cations form six‐mem‐bered Be₃O₃ rings with boat conformation and distorted tetrahedrally coordinated beryllium atoms with the terminally coordinated H₂O molecules. The structure ist characterized by a complicated three dimensional hydrogen‐bridging network including O–H ··· O, O–H ··· Cl, and O–H ··· NCCH₃ contacts. DFT calculations result in nearly planar [Be₃(OH)₃] six‐membered ring conformations.     

Synthese und Kristallstruktur des heterobimetallischen Diorganozinndichlorids (FcN,N)2SnCl2 (FcN,N—: (η5‐C5H5)Fe{(η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}—)

Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)₂SnCl₂ (FcN, N^—: (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2}^—) The heterobimetallic title compound [(FcN, N)₂SnCl₂] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl₄ in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N^— ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N^— remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P2₁/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1_obs· = 0.051, wR2_obs· = 0.136.     

Octa­hedral–tetra­hedral framework structures of InAsO4·H2O and PbIn(AsO4)(AsO3OH)

Indium arsenate(V) monohydrate, InAsO₄·H₂O, (I), crystallizes in the structure type of MnMoO₄·H₂O. The structure is built of In₂O₈(H₂O)₂ dimers (mean In—O = 2.150 Å) corner‐linked to slightly distorted AsO₄ tetra­hedra (mean As—O = 1.686 Å). The linkage results in a three‐dimensional framework, with small voids into which the apical water ligand of the InO₅(H₂O) octa­hedron points. The hydrogen bonds in (I) are of medium strength. Lead(II) indium arsenate(V) hydrogen arsenate(V), PbIn(AsO₄)(AsO₃OH), (II), represents the first reported lead indium arsenate. It is characterized by a framework structure of InO₆ octa­hedra corner‐linked to AsO₄ and AsO₃OH tetra­hedra. The resulting voids are occupied by Pb₂O₁₀(OH)₂ dimers built of two edge‐sharing highly distorted PbO₆(OH) polyhedra (mean Pb—O = 2.623 Å). The compound is isotypic with PbFe^III(AsO₄)(AsO₃OH). The average In—O bond length in (II) is 2.157 Å. In both arsenates, all atoms are in general positions.     

Synthese und Charakterisierung von 2‐O‐funktionalisierten Ethylrhodoximen und ‐cobaloximen

Synthesis and Characterization of 2‐O‐Functionalized Ethylrhodoximes and ‐cobaloximes 2‐Hydroxyethylrhodoxime and ‐cobaloxime complexes L—[M]—CH₂CH₂OH (M = Rh, L = PPh₃, 1 ; M = Co, L = py, 2 ; abbr.: L—[M] = [M(dmgH)₂L] (dmgH₂ = dimethylglyoxime, L = axial base) were obtained by reaction of L—[M]^— (prepared by reduction of L—[M]—Cl with NaBH₄ in methanolic KOH) with BrCH₂CH₂OH. H₂O—[Rh]^—, prepared by reduction of H[RhCl₂(dmgH)₂] with NaBH₄ in methanolic KOH, reacted with BrCH₂CH₂OH followed by addition of pyridine yielding py—[Rh]—CH₂CH₂OH ( 3 ). Complexes 1 and 3 were found to react with (Me₃Si)₂NH forming 2‐(trimethylsilyloxy)ethylrhodoximes L—[Rh]—CH₂CH₂OSiMe₃ (L = PPh₃, 4 ; L = py, 5 ). Treatment of complex 1 with acetic anhydride resulted in formation of the 2‐(acet oxy)ethyl complex Ph₃P—[Rh]—CH₂CH₂OAc ( 6 ). All complexes 1 — 6 were isolated in good yields (55—71 %). Their identities were confirmed by NMR spectroscopic investigations ( 1 — 6 : ¹H, ¹³C; 1 , 4 , 6 : ³¹P) and for [Rh(CH₂CH₂OH)(dmgH)₂(PPh₃)]·CHCl₃·1/2H₂O ( 1 ·CHCl₃·1/2H₂O) and py—[Rh]—CH₂CH₂OSiMe₃ ( 5 ) by X‐ray diffraction analyses, too. In both molecules the rhodium atoms are distorted octahedrally coordinated with triphenylphosphine and the organo ligands (CH₂CH₂OH and CH₂CH₂OSiMe₃, respectively) in mutual trans position. Solutions of 1 in dmf decomposed within several weeks yielding a hydroxyrhodoxime complex “Ph₃P—[Rh]—OH”. X‐ray diffraction analysis exhibited that crystals of this complex have the composition [{Rh(dmg)(dmgH) (H₂O)(PPh₃)}₂]·4dmf ( 7 ) consisting of centrosymmetrical dimers. The rhodium atom is distorted octahedrally coordinated. Axial ligands are PPh₃ and H₂O. One of the two dimethylglyoximato ligands is doubly deprotonated. Thus, only one intramolecular O—H···O hydrogen bridge (O···O 2.447(9)Å) is formed in the equatorial plane. The other two oxygen atoms of dmgH^— and dmg^2—, respectively, act as hydrogen acceptors each forming a strong (intermolecular) O···H′—O′ hydrogen bridge to the H′₂O′ ligand of the other molecule (O···O′ 2.58(2)/2.57(2)Å).     

Darstellung und Kristallstruktur von HgPb2O(OH)Br3

Inhaltsübersicht. Die erstmals dargestellte Verbindung HgPb₂O(OH)Br₃ kristallisiert orthorhombisch in der Raumgruppe Aba2 (Nr. 41) mit den Gitterkonstanten a = 14,652(3) Å, b = 14,6491(8) Å, c = 7,782(2) Å und Z = 8. Die Bestimmung der Kristallstruktur mit Einkristallmethoden zeigte “isolierte”, verzerrt würfelförmige Baugruppen der Zusammensetzung [Hg₂Pb₄O₂(OH)₂]. Diese Einheiten werden von Bromidionen umhüllt. HgPb₂O(OH)Br₃ stellt damit hinsichtlich des strukturellen Aufbaus ein Bindeglied zwischen den Verbindungen [Pb₄(OH)₄](ClO₄)₄ · 2H₂O [1] und Pb₉O₄Br₁₀ [2] dar. Preparation and Crystal Structure of HgPb₂O(OH)Br₃ The new compound, HgPb₂O(OH)Br₃ was prepared and investigated by X-ray crystal structure analysis. Crystals of orthorhombic symmetry show space group Aba2 (No. 41) with lattice parameters a = 14.652(3) Å, b = 14.6491(8) Å, c = 7.782(2) Å, and Z = 8. Remarcable structural units with heterocubane skeleton were found. The [Hg₂Pb₄O₂(OH)₂] group forms a new member of the structural class between [Pb₄(OH)₄] and [Pb₈O₄] units with the relating compounds [Pb₄(OH)₄)](ClO₄)₄ · 2 H₂O [1] und Pb₉O₄Br₁₀ [2].     

Das erste Vanadium(III)‐Borophosphat: Darstellung und Kristallstruktur von CsV3(H2O)2[B2P4O16(OH)4]

The First Vanadium(III) Borophosphate: Synthesis and Crystal Structure of CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] was prepared under mild hydrothermal conditions (T = 165 °C) from mixtures of CsOH_(aq), VCl₃, H₃BO₃, and H₃PO₄ (molar ratio 1 : 1 : 1 : 2). The crystal structure was determined by X‐ray single crystal methods (monoclinic; space group C2/m, No. 12): a = 958.82(15) pm, b = 1840.8(4) pm, c = 503.49(3) pm; β = 110.675(4)°; Z = 2. The anionic partial structure contains oligomeric units [BP₂O₈(OH)₂]^5–, which are built up by a central BO₂(OH)₂ tetrahedron and two PO₄ tetrahedra sharing common corners. V^III is octahedrally coordinated by oxygen of adjacent phosphate tetrahedra and OH groups of borate tetrahedra as well as oxygen of phosphate tetrahedra and H₂O molecules, respectively (coordination octahedra VO₄(OH)₂ and VO₄(H₂O)₂). The oxidation state +3 for vanadium was confirmed by measurements of the magnetic susceptibility. The trimeric borophosphate groups are connected via vanadium centres to form layers with octahedra‐tetrahedra ring systems, which are likewise linked via V^III‐coordination octahedra. Overall, a three‐dimensional framework constructed from VO₄(OH)₂ and VO₄(H₂O)₂ octahedra as well as BO₂(OH)₂ and PO₄ tetrahedra results. The structure contains channels running along [001], which are occupied by Cs⁺ in a distorted octahedral coordination (CsO₄(H₂O)₂).     

A Sterically Hindered Phosphonic Acid with a Hydrogen‐Bonded Cage Structure: [4‐tert‐Bu‐2,6‐Mes2‐C6H2P(O)(OH)2·H2O]4

The synthesis and molecular structure of the novel phosphonic acid 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂P(O)(OH)₂ ( 1 ) is reported. Compound 1 crystallizes in form of its monohydrate as a hydrogen‐bonded cluster ( 1·H₂O )₄ comprizing four phosphonic acid molecules (O···O 2.383(3)‐3.006(4) Å). Additionally, sterically hindered terphenyl‐substituted phosphorus compounds of the type 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂PR(O)(OH) ( 5 , R = H; 7 , R = O₂CC₆H₄‐3‐Cl; 9 , R = OEt) were prepared, which all show dimeric hydrogen‐bonded structures with O···O distances in the range 2.489(2)–2.519(3) Å. Attempts at oxidizing 5 using H₂O₂, KMnO₄, O₃, or Me₃NO in order to give 1 failed. Crystallization of 5 in the presence of Me₃NO gave the novel hydrogen bonded aggregate 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂PH(O)(OH)·ONMe₃ ( 6 ) showing an O–H···O distance of 2.560(4) Å.     

Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]– (R = iBu,iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K‐18c6)Au[Ge9{Si(iBu)3}3]2, and (K‐18c6)2[Ge9{Si(iBu)3}2]

Novel silylation reactions at [Ge₉] Zintl clusters starting from the chlorosilanes SiR₃Cl (R = iBu, iPr, Et) and the Zintl phase K₄Ge₉ are reported. The formation of the tris‐silylated anions [Ge₉(SiR₃)₃]^– [R = iBu ( 1a ), iPr ( 1b ), Et ( 1c )] by heterogeneous reactions in acetonitrile was monitored by ESI‐MS measurements. For R = iBu ¹H, ¹³C and ²⁹Si NMR experiments confirmed the exclusive formation of 1a . Subsequent reactions of 1a with CuNHC^DippCl and Au(PPh₃)Cl result in formation of the neutral metal complex (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃]·0.5 tol ( 2 ·0.5 tol) and the metal bridged dimeric unit {Au[Ge₉{Si(iBu)₃}₃]₂}^– ( 3a ), isolated as a (K‐18c6)⁺ salt in (K‐18c6)Au[Ge₉{Si(iBu)₃}₃]₂·tol ( 3 ·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18‐crown‐6, crystals of the compound (K‐18c6)₂[Ge₉{Si(iBu)₃}₂]·tol ( 4 ·tol), containing the bis‐silylated cluster anion [Ge₉(Si(iBu)₃)₂]^2– ( 4a ), were obtained. The compounds 2 ·0.5 tol, 3 ·tol and 4 ·tol were characterized by single‐crystal structure determination.