Caught by the cage: New vanadium phosphonate cages with a fluoride template inside and charge-compensating transition-metal cations outside were prepared in a simple way. The charge and ligand sphere of the cation govern its interaction with the cage and can be used to modify the magnetic and redox properties of the cage, which also depend on the anionic template (see figure). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

A new and simple preparation method for fluoride-templated tetranuclear vanadium phosphonate cage compounds, M(n+)[(V2O3)2(RPO3)4<F]n is outlined. The crystalline products were characterized by X-ray diffraction, elemental analysis, and thermogravimetric analysis. Using the acceptable solubility of the products, multinuclear NMR could be performed on the corresponding solutions. Some insight into the process of formation of the cage compounds in solution could be reached by monitoring the corresponding reaction mixture by multinuclear NMR. The template function of the F(-) ion could be demonstrated together with the fact that the non-transition-metal ions (M(n+)) used here (phosphonium ions) have no direct effect on the formation of the cage. In contrast, the redox behavior of these compounds in the solid state distinctly depends on the cations. This could be easily investigated by electron paramagnetic resonance because the mixed-valence species (3V(V)/V(IV)) can be produced chemically or thermally induced in solution as well as in the solid state. In the latter case, the reaction of the cage with H2 activated on the platinum powder can be regarded as a key experiment for understanding the redox process of the title compounds in the solid state. The role of specific interactions in solution at the tumbling rate and the localization of spin density in the cage could be demonstrated by the reduction performed with 1-methylimidazole and quinoline. While the substituents R = Me and Ph have only a small influence on the cage formation in solution, they have a significant influence on the redox reaction and structural relaxation in the solid state.

Solvothermal syntheses at 373 K in the system MePPh3)[VO2Cl2]/ RPO3H2 (R = tBu; Ph)/Template (T = Cl-, HCl, OH-; Br-) /MeCN have lead to the already known compound [(VO)(6)(tBuPO(3))(8) subset of Cl-] (1) [1] as well as to [(VO)(6)-(tBuPO(3))(8) subset of T](T: HCl (2) OH- 3), [(VO)(6)(PhPO3)(8) subset of Br-]Xsolv (4), (Ph3PMe)(2)[(VO)(6)(PhPO3)(8) subset of Cl-](3) (5) with an identical VPO-core, and [(V3O5)(VO)(4)(tBuPO(3))(8) subset of NO3-] (6) with seven metal centres. The renewed X-ray structure analysis of 1 produced evidence, that the {V6P8O24}-core shows some flexibility and belongs to the enantiomorphic point group O ( 432). With the structure data from the compounds 1-5 a geometric model for the flexible contraction of the {V6P8O24}-core was developed. The calculation of the diameter of the host shell for different degrees of contraction shows that the {V6P8O24}-core is always too small to incorporate a nitrate ion. This leads to the formation of [(V3O5)(VO)(4)(tBuPO(3))(8) subset of NO3-] (6) which can be derived topologically from 1. There is no structural similarity between 6 and the seven oxovanadium units containing anion of (Ph4P)(2)[(V4O7)(V3O5)(PhPO3)(6) subset of Cl-] [2]. The thermal degradation of I in air starts at 590 K with the oxidation of the organic groups followed by the formation of beta-(VO)(PO3)(2). Possibly these results offer new ways to use oxovanadium phosphonates as precursors of oxovanadium phosphate catalysts.

Anpassungsfähig: Vanadiumkäfige mit F− als Templat wie der im Bild gezeigte bieten einzigartige Möglichkeiten zur Anpassung ihrer Eigenschaften und zeigen ein unerwartetes Redoxverhalten gegen NO und H2: Sie reagieren im Singulettzustand mit beiden Verbindungen, wenn sie an mit Ag+ bedeckten γ-Al2O3-Oberflächen adsorbiert sind, unter Bildung des gemischtvalenten Zustands des Vanadiumkäfigs. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2007/z701211_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Highly adaptable: Vanadium cage compounds templated on F− (see picture) offer unique possibilities for tuning properties and exhibit unexpected redox behavior with respect to NO and H2. When adsorbed on the surface of γ-Al2O3 coated with Ag+, they react in the singlet state with both NO and H2. In both cases, the vanadium mixed-valence state of the cage could be identified by EPR spectroscopy. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z701211_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Based on XRD and optimized structures of the cage compound [(V2O3)2(PhPO3)4CF]-n in singlet (n = 1) and doublet (n = 2) states DFT calculations were carried out to determine the energies and spin density distribution for the symmetries D-2d, C-2, and C-s It turned out, that the cage with C, symmetry not only represents the energetically more stable doublet system (with respect to D2d and C2,-symmetries) but also corresponds to the real compound under study, The SOMO of the S = 1/2 cage represents an antibonding state and the volume of the cage in this state is larger than that in the S = 0 state. The calculated ESR hyperfine coupling constants are in acceptable agreement with those determined by ESR. Experimentally the localization/delocalization of spin density was determined via ESR as a function of temperature and adsorption of the cage on Al2O3, respectively. A proposal is given for the localization/delocalization of spin density based on thermally driven changes of the cage symmetry in combination with the hopping of the impaired electron inside the cage. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).

AbstractSynthesis, Characterization, and Structure of the Donor‐stabilized Monomeric [PS3]− Anion (Monometatrithiophosphate)The reaction between H2S and some σ4λ5‐derivatives of the monometa‐dithioxaphosphoric acid, [Py→PS2X] (Py = pyridine, X = Cl, NR2), at low temperature in propionitrile as a solvent leads to the formation of the corresponding ammonium salts with the new anion [Py→PS3]− (1). The single crystal structure determinations of three compounds 1a‐1c bearing the new title anion 1 reveal the existence of considerably short distances between the nitrogen of the cation and the sulphur atoms of the anion connected by a cationic proton in all cases. These hydrogen bond contacts fall below the sum of van der Waals radii of nitrogen and sulphur and are crucial for the stabilization of 1 in the crystals which is an electronical support in nature. If acidic hydrogen atoms are not present in the cations of the salts as in the case of tetraphenylarsonium as a counter cation a stabilisation of the new anion 1 does not occur. In this case, even from pyridine solutions, only the salt with the well known dimeric anion [PS3]22− crystallizes.

The reaction between H2S and some sigma(4)lambda(5)-derivatives of the monometa-dithioxaphosphoric acid, [PY -> PS2X] (Py = pyridine, X = Cl, NR2), at low temperature in propionitrile as a solvent leads to the formation of the corresponding ammonium salts with the new anion [PY -> PS3](-) (1). The single crystal structure determinations of three compounds 1a-1c bearing the new title anion I reveal the existence of considerably short distances between the nitrogen of the cation and the sulphur atoms of the anion connected by a cationic proton in all cases. These hydrogen bond contacts fall below the sum of van der Waals radii of nitrogen and Sulphur and are crucial for the stabilization of I in the crystals which is an electronical support in nature. If acidic hydrogen atoms are not present in the cations of the salts as in the case of tetraphenylarsonium as a counter cation a stabilisation of the new anion I does not occur. In this case, even from pyridine solutions, only the salt with the well known dimeric anion [PS3](2-)(2) crystallizes.

Phosphorus-31 magic-angle spinning NMR spectroscopy was chosen in order to study a series of N-donor stabilized dithiomonometaphosphoryl halides (F, Cl, and Br) and to extract structural and bonding information from their spectra. Additionally, an unusual line splitting was observed in the 31P MAS NMR spectra of pyridine dithiomonometaphosphoryl chloride (Py→PS2Cl) and the analogous bromide (Py→PS2Br). It is shown that this effect is due to a residual dipolar coupling between phosphorus and chlorine or bromine, respectively. This work is to our knowledge the first observation of this effect between P and Br in 31P MAS NMR spectra.

Dialkylamide derivatives of the monometadithioxaphosphoric acid stabilised by pyridine as a donor, i.e. [(C5H5N)PS2NR2], readily react with AlCl3. The elimination of the donor and formation of the adduct (C5H5NAlCl3)-Al-. liberates the unstable sigma(3)lambda(5)-phosphoranes (PS2NR2). The latter are stabilised by [2+2] "cycloaddition-dimerization" leading to the title compounds [PS2NR2](2) in nearly quantitative yields. The synthesis and characterisation of two compounds possessing NR2 substituents of very different basicities clearly demonstrate the generalisation of such a procedure as an easy way of accessing further derivatives in this class. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

By reaction of boron phosphate, BPO4, and vanadium(IV)-oxide, VO2, at 1050 degreesC a hitherto unknown vanadium(III)-borophosphate is formed. Its composition was found to be V2BP3O12, its structure was elucidated by single crystal X-ray diffraction, the cell parameters are: a = b = 13.9882 Angstrom; c = 7.4515 Angstrom; alpha = beta = 90degrees, gamma = 120degrees; Z = 6; space group: P6 3/m. Noteworthy features of the structure are V2O9 units (two (VO6)-O-III octahedra connected via their faces) and isolated trisphosphatoborate groups, B(PO4)(3). By shared oxide ions, the aforementioned groups are interconnected, thus forming a three dimensional network. The structural relation between the title compound and an analogous chromium compound is discussed.

The first transition-metal (Rh(I), Mo(VI), Ni(II)) complexes of S[double bond, length as m-dash]P(NHBu(t))(3) have been synthesized via metathetical reactions of mono-lithiated and [Rh(CO)(2)Cl](2), (Bu(t)N)(2)MoCl(2)(dme) and NiBr(2)(dme). Surprisingly in the molecular structure of the Ni(II)-complex both hard-soft (N,S) and hard-hard (N,N[prime or minute]) chelation modes of are realized.

AbstractDie vor einer Reihe von Jahren experimentell bei Reorganisationsreaktionen zwischen P4S10 und P4O10 gefundene Stabilität von Isomeren der Phosphoroxidsulfide der allgemeinen Formel P4O10—nSn wurde durch Dichtefunktionaltheorie(DFT)‐Rechnungen bestätigt. Die erhaltenen Daten lassen auch Aussagen über die Chancen einer erfolgreichen Darstellung bisher noch nicht isolierter oder unzureichend charakterisierter Phosphoroxidsulfid‐Isomere zu.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Angewandte ChemieVolume 115, Issue 22 p. 2588-2590 Zuschrift Das erste Ozonid eines Phosphoroxids – Synthese, Charakterisierung und Kristallstruktur von P4O18† Anton Dimitrov Dr., Anton Dimitrov Dr. Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Deutschland, Fax: (+49) 30-2093-7468Search for more papers by this authorBurkhard Ziemer Dr., Burkhard Ziemer Dr. Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Deutschland, Fax: (+49) 30-2093-7468Search for more papers by this authorWolf-Dietrich Hunnius Dr., Wolf-Dietrich Hunnius Dr. Institut für Anorganische und Analytische Chemie, Freie Universität Berlin, Fabeckstraße 34–36, 14195 Berlin, DeutschlandSearch for more papers by this authorManfred Meisel Prof. Dr., Manfred Meisel Prof. Dr. manfred.meisel@chemie.hu-berlin.de Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Deutschland, Fax: (+49) 30-2093-7468Search for more papers by this author Anton Dimitrov Dr., Anton Dimitrov Dr. Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Deutschland, Fax: (+49) 30-2093-7468Search for more papers by this authorBurkhard Ziemer Dr., Burkhard Ziemer Dr. Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Deutschland, Fax: (+49) 30-2093-7468Search for more papers by this authorWolf-Dietrich Hunnius Dr., Wolf-Dietrich Hunnius Dr. Institut für Anorganische und Analytische Chemie, Freie Universität Berlin, Fabeckstraße 34–36, 14195 Berlin, DeutschlandSearch for more papers by this authorManfred Meisel Prof. Dr., Manfred Meisel Prof. Dr. manfred.meisel@chemie.hu-berlin.de Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Deutschland, Fax: (+49) 30-2093-7468Search for more papers by this author First published: 05 June 2003 https://doi.org/10.1002/ange.200351135Citations: 7 † Diese Arbeit wurde durch den Fonds der Chemischen Industrie gefördert. A.D. dankt der öffentlichen Hand für die seit 1992 gewährte finanzielle Unterstützung im Rahmen der Integrationsprogramme für die evaluierten Wissenschaftler der ehemaligen Akademie der Wissenschaften der DDR. Wir danken Dr. A.-R. Grimmer für die Festkörper-NMR-spektroskopischen Untersuchungen. Read the full textAboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract Es gibt sie doch, aber anders: binäre Peroxoverbindungen des Phosphors. Während das von Schenk 1937 beschriebene Peroxid P2O6 nach wie vor nur als Vermutung existiert, wurde durch Reaktion von Ozon mit Phosphor(III)-oxid bei tiefen Temperaturen mit dem Tetraozonid P4O18 (siehe Struktur) erstmals eine definierte Peroxoverbindung des binären Systems Phosphor/Sauerstoff hergestellt. Diese bisher sauerstoffreichste Verbindung des Phosphors könnte als Quelle für Singulettsauerstoff unter sehr milden Bedingungen eingesetzt werden. Citing Literature Volume115, Issue22June 6, 2003Pages 2588-2590 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. RelatedInformation

A specific force field of Consistent Valence Force Field type was developed with the aim to simulate the structures of catalysts of vanadium phosphorus oxide type and the reversible adsorption of organic compounds on specific crystallographic planes of such catalysts by molecular modeling. The appropriate parameters were derived for the bonded (stretching, bending, and torsional deformations) and nonbonded (attractive and repulsive van der Waals and Coulomb forces) atomic interactions for V - O and P - O bonds in typical fragments of these catalysts with the vanadium atom in the oxidation state IVThe parameters for bonded interactions were computed from Hessian matrices, supplied by the program DMol for performing Density Functional Theory, by means of a program for non-linear regression.The DMol program was applied to energy minimize structures of known vanadium phosphorus oxides, which were compared with X-ray structures, and to obtain their Hessian matrices as a basis for the force constants needed. Some hypothetical structural models had to be added. The van der Waals parameters were estimated by means of correlations between van der Waals radii and the repulsive parameters and between polarizabilities and the dispersive parameters from the literature. The force field obtained was applied to simulate the crystal structure of vanadyl pyrophosphate and to compute the heat of adsorption of n-butane and of 1-butene on its (100) plane (computer codes of company Biosym/MSI/Accelrys). The experimental crystal structure and the adsorption energies were fairly well reproduced, except that the a lattice constant proves somewhat too large(1)).

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The title compounds, ethyldiphenylphosphine-dithiomonometaphosphoryl chloride, EtPh(2)P-->PS(2)Cl, C(14)H(15)ClP(2)S(2), (I), and tris-n-propylphosphine-dithiomonometaphosphoryl chloride and bromide, nPr(3)P-->PS(2)Cl, C(9)H(21)ClP(2)S(2), (II), and nPr(3)P-->PS(2)Br, C(9)H(21)BrP(2)S(2), (III), respectively, are the first phosphine-stabilized dithiomonometaphosphoryl halides to be structurally characterized. In the tris-n-propylphosphine derivatives, the central P-->P donor-acceptor bond becomes longer in the order bromo < chloro < fluoro. Substitution of the tris-n-propylphosphine group in (II) by the more bulky ethyldiphenylphosphine group also leads to a longer P-->P bond. These structural features agree with the observed 31P NMR data. In (II) and (III), the central P-P bond coincides with the crystallographic threefold axis, entailing site-occupational disorder for the S(2)Y group.

The reactivity of the donor-stabilized monometaphosphoryl chloride Py⇒PS2Cl (1) versus multiple bond systems and organometallic compounds has been studied. Thus, on the reaction of 1 with diphenyl acetylene at elevated temperature the five-membered ring systems 2–4 are formed. In the first step probably cycloaddition of the intermediary liberated free monometaphosphoryl chloride PS2Cl with diphenyl acetylene leads to the 1-thia-phosphacyclobut-3-ene 6. This assumption will be supported by theoretical calculations. Attempts to eliminate one sulfur atom from the disulfide bridge in 2 result in the bicyclic ring system 5 besides a compound which is assumed to be 6. The reaction of 1 with tertBuLi gives the dithiaphosphetane 7 whereas with NaN(SiMe3)2 the diazadiphosphetidine 8 is obtained.

The title compound, C12H27PS, has crystallographic C3 symmetry. The bond angles at phosphorus are tetrahedral [C--P--S 109.31 (12) degrees and C--P--C 109.63 (12) degrees ] and the P--C bond length is 1.899 (4) A. The shortest intermolecular contacts exist between methyl H atoms and the S atom (3.09, 3.12 and 3.28 A). A survey of various phosphine sulfides containing three equal ligands (Me3PS, Et3PS, Cy3PS, tBu3PS, etc.) shows the influence of substituents with different steric demand on the geometry at phosphorus and on the P--C bond length.