Mass spectra of monohapto-cyclopentadienyl derivatives of group IVB elements

Dissociative ionisation of organometallic cyclopentadiene derivatives containing one, two or three M(CH₃)₃ groups (M  Si, Ge, Sn) has been studied.Among the monometallated compounds, C₅H₅Si(CH₃)₂Cl, C₅H₅Si(CH₃)₂OCH₃ and (C₅H₅)₄Sb have also been investigated. To verify fragmentation patterns, the spectra of deuterated compounds such as C₅D₅Si(CH₃)₃, C₅D₅Sn(CH₃)₃, C₅D₄Si₂(CH₃)₆ and C₅D₃Si₃)₉ have been measured. Dissociative ionisation of h¹-cyclopentadienyl derivatives has been shown to differ essentially from that of h⁵-compounds.     

Organische Phosphorverbindungen XXXVIII. Darstellung und Eigenschaften von Tris-(dialkoxyphosphonyl-methyl)-, Tris-(alkoxyphosphinyl-methyl)-und Tris-(oxophosphoranyl-methyl)-phosphinsäureestern sowie der entsprechenden Säuren [1]

Tris-chloromethyl-phosphine oxide, (ClCH₂₎₃ P?O(I), is obtained by chlorination of (HOCH₂₎₃P?O with PCl₅ or (C₆H₅₎₃PCl₂, and also by oxidation of (CICH₂₎₃P?O and (ClCh₂₎₂(CH₃)P?O. High yields of tris-(dialkyloxyphosphonly-methyl)-phosphine oxides, [RO₂(O)PCH_2]2P?O (II) (R?CH₃, C₂H₅, iso-C₃H₇, n-C₄H₉, 2- ethyl-hexyl), tris (alkyloxyphosphinyl-methyl)-phosphine oxides, [R₂(O)PCH_2]3P?O(R = C₆H₅, CH₃) are obtained by heating tris-chloromethyl-phosphine oxides, [(RO) (R′) (O)PCH_2]3P?O (R = C₄H₉, R′? C₆H₅) and tris-(oxophosphoranyl-phosphine oxides with phosphites, phosphonites and phosphinites, respectively, at 170–180°C for several hours. Compounds II possess an extraordinarily high absorption capacity. Thus a warm. 2% solution of II (R = C₂H₅) in benzene solidifies completely on cooling so that no benzene can be poured off. Tris-dihydroxyphosphonyl-methyl)-phosphine oxide, [(HO)₂(O)PCH_2]3P?O, obtained by hydrolysis of II (R ? C₂H₅) with refluxing conc. HCl or by thermal decomposition of II (R ? iso-C₃H₇) at 190°, titrates in aqueous solution as a hexabasic acid with breaks at pH = 4,4 (three equivalents) and pH = 10,7 (three equivalents). It forms crystalline salts with amines, alkali and alkaline earth metals, and is an excellent chelating agent. The ¹H- and ^31?P-NMR. spectra of all the compounds prepared are discussed.     

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).     

Synthesis,characterization and biological studies on unsymmetrical Schiff-base complexes of nickel(II), copper(II) and zinc(II) and adducts with 2,2′-dipyridine and 1,10-phenanthroline

A series of metal(II) unsymmetrical Schiff-base complexes, {M(C₁₀H₆OCH:N(CH₂)₂N?:?C(CH₃)CH?:?C(CH₃)O), where M=Ni(II), Cu(II) and Zn(II)}, and their 2,2′-dipyridine (bipy) and 1,10-phenanthroline (phen) adducts are synthesized and characterized by microanalysis, magnetic susceptibility, conductance, IR and UV-Vis spectra. The ligand coordinates using the N₂O₂ chromophore to give a two-metal-center four-coordinate square-planar geometry. IR and UV-Vis spectra are consistent with octahedral adducts. The compounds are non-electrolytes in nitromethane and magnetic moments indicate that the complexes are magnetically dilute. The antimicrobial activity of the compounds against ten bacteria and one fungus are reported. The Cu(II) and Zn(II) complexes showed good activity against many of the organisms while their adducts are generally not sensitive. The minimum inhibitory concentrations (MICs) of the sensitive compounds are between 3.0–13.0?mg?mL^?1.     

Dichlorophosphate zweiwertiger Übergangsmetalle von Mangan,Eisen, Kobalt,Nickel und Kupfer

Dichlorophosphates of the Divalent Transition Metals Manganese, Iron, Cobalt, Nickel, and Copper The dichlorophosphates M(O₂PCl₂)₂ · 2 POCl₃ with M = Mn, Fe, Ni and Co(O₂PCl₂)₂ are prepared from the metal acetates and POCl₃, whereas Cu(O₂PCl₂)₂ only yields from the formiate and P₂O₃Cl₄. The finely distributed metals Fe, Co, and Ni react with excess dichlorophosphoric acid. forming the complexes M(O₂PCl₂)₂ · 2 HOPOCl₂. According to the vibrational spectra, the metal atoms are linked to polymeric 8-ring structures by O? P? O bridges. Moreover the dichlorophosphoric acid solvates are stabilized by hydrogen bridges.     

Über die Umsetzung von Adipinsäurediamid mit Phosphorpentachlorid

Reaction of Adipic Acid Diamide with Phosphorus Pentachloride The reaction of adipamide (I) with phosphorus pentachloride in a solvent leads to (Cl₃P?NCCl₂CCl₂CH₂)₂ (II). The stages of the reaction are: 1. chlorination of the keto and methylen groups 2. formation of the ? N?PCl₃ group. This result is a supplement of the existing conception about the course of the reaction of carboxylic acid amides with phosphorus pentachloride. The reaction of (I) with PCl₅ without any solvent has been reproduced and the course of reaction has also been investigated. This reaction gives mainly NC(CH₂)₄CN. The resulting product of a careful hydrolysis of (II) is (Cl₂OPN?CClCl₂CH₂)₂. A total hydrolysis gives back (I).     

10‐Methyl‐ and 9,10‐dimethyl­acridinium methyl sulfate

The title compounds, C₁₄H₁₂N⁺·CH₃O₄S^?, (I), and C₁₅H₁₄N⁺·CH₃O₄S^?, (II), respectively, crystallize with the planar 10‐methylacridinium or 9,10‐di­methyl­acridinium cations arranged in layers, parallel to the twofold axis in (I) and perpendicular to the 2₁ axis in (II). Adjacent cations in both compounds are packed in a `head‐to‐tail' manner. The methyl sulfate anion only exhibits planar symmetry in (II). The cations and anions are linked through C—H?O interactions involving three O atoms of the anion, six acridine H atoms and the CH₃ group on the N atom in (I), and the four O atoms of the anion, three acridine H atoms and the carbon‐bound CH₃ group in (II). The methyl sulfate anions are oriented differently in the two compounds relative to the cations, being nearly perpendicular in (I) but parallel in (II). Electrostatic interaction between the ions and the network of C—H?O interactions leads to relatively compact crystal lattices in both structures.     

Dimethylzinndithioquadratat: Die Kristallstruktur des Benzol-Solvats und des Dimethylsulfoxid-Addukts

Dimethyltin Dithiosquarate: The Crystal Structure of the Benzene Solvate and of the Dimethylsulfoxide Adduct (CH₃)₂SnS₂C₄O₂ · 1/3 C₆H₆ ( I ) crystallizes in the orthorhombic space group Pnma. a = 14.393(2), b = 21.668(3), c = 10.424(1) Å, Z = 12. (CH₃)₂SnS₂C₄O₂ · (CH₃)₂SO ( II ) is monoclinic, space group P2₁/n, a = 9.918(5), b = 12.028(6), c = 12.223(6) Å, β = 108.82(3)°, Z = 4. In I there are two independent dimethyltin dithiosquarate molecules. But in both molecules the Sn atoms display weak coordinative bonds to two O atoms of adjacent dithiosquarate groups. The distances amount 2.873 Å (2×), resp. 2.678 and 2.831 Å. The coordination number of tin becomes 6 and the structure gets connected in three dimensions. In II dimethylsulfoxide is bound with the O atom to Sn (2.345 Å) and the result is a distorted trigonal bipyramid. There a more distant O atom (2.944 Å) leads to a connection of the molecules to a ribbon. The changes of the geometrical parameters are described, which result from the progressive approach of the one O atom.     

Die Kristall- und Molekülstruktur von (CH3)2SnSAB (SAB = Dianion von 2-Hydroxy-N-(2-hydroxybenzyliden)-anilin)

Crystal and Molecular Structure of (CH₃)₂SnSAB. (SAB = Dianion of 2-Hydroxy-N-(2-hydroxybenzylidene)-aniline) (CH₃)₂SnSAB, C₁₅H₁₅NO₂Sn (SAB = tridentate dianion of 2-hydroxy-N-(2-hydroxybenzylidene)-aniline in SCHIFF base form) crystallizes in the space group Pben (D) with a = 19.271(5), b = 10.508(2), c = 13.379(1) Å and Z = 8. The structure has been solved using 1307 symmetrical independent reflections and applying the heavy atom method; the position of all atoms, except the H atoms, has been determined. As interatomic distances have been found: Sn? C: 2.117(14), Sn? O:2.112(9), Sn? N:2.229(11) N? C 10 (phenyl group II): 1.462(16), C9-N (SCHIFF base bridging group): 1.257(18), C 9? C8 (phenyl group I): 1.441(18) Å; mean C? C distances in the phenyl groups: 1.403(18) Å. Two molecules at a time have a centre of symmetry and weakly coordinate through two loose Sn? O bridges (intermolecular Sn? O distance: 2.881(8) Å). The individual molecules essentially form a distorted trigonal bipyramid with N and both methyl-C atoms in the equatorial plane; ? CSnC = 138.52(50)°; ? OSnO = 158.58(35)°.     

Synthese und XPS-Analyse von nano-skaligen Metall/Metalloxid-Kompositen mit Germanium,Zinn und Blei als metallische Komponente

Synthesis and XPS Analysis of nano-scaled Metal/Metaloxid Composites with Germanium, Tin, and Lead as Metallic Component tert-Butanolates of Germanium(II), tin(II), and lead(II) of the formula {M[O-C(CH₃)₃]₂}_n (M ? Ge, n = 2; M ? Sn, n = 2; M ? Pb, n = 3) as well as the corresponding heterometalalkoxides M′M₂[O? C(CH₃)₃]₆ (M ? Ge, M′ ? Sr, Ba; M ? Sn, M′ ? Ca, Sr, Ba; M ? Pb, M′ ? Ca, Ba) have been subject to a single precursor chemical vapour deposition (CVD) process. In this process the volatile precursor has been pyrolized under reduced pressure (0,1 Torr) on a graphit or metal substrate which has been heated by induction in a microwave field to about 300–500°C. The gases originating from this pyrolisis have been analyzed by means of a quadrupole mass spectrometer whereas the solid coating which contained the micro composite was characterized by X-ray diffraction, electron microscopy, EDX-analysis and XPS-spectra. In all cases the solid material contained two phases, in which the element M ((Ge), Sn, Pb) either had oxidation state 0 or +4 (in the surface of the solids made of germanium containing precursors only Ge^II along with Ge⁰ has been detected by XPS spectroscopy). The group 14-element in the starting material had thus undergone a disproportionation from the +2 oxidation state into a lower and a higher one by two units. The elemental phase and the phase containing the formal +4 cation which is amorphous in most cases and which approaches the formula MO₂ or M′MO³ (M ? (Ge), Sn, Pb; M′ ? Ca, Sr, Ba) are uniformally distributed. The composites consist of ball shaped particles on which other smaller particles are placed in a fractal manner ressembling a black berry. In the case of the composite Sn · BaSnO³ the center of the ball shaped particles has been analyzed as pure elemental tin. The organic substituents of the precursors as well as the dynamic vacuum in the decomposition process seem to be responsible for the ball shaped nature of the solid material. In a test experiment gallium tri-tert-but-oxide has been used as precursor: again ball shaped particles are obtained which have the chemical composition Ga₂O₃ but which contain no elemental gallium.     

Über Phosphorstickstoffverbindungen,XXXII. Über Vier- und fünfgliedrige Heterocyclen mit Phosphor,Stickstoff und Kohlenstoff im Ring

On reacting of oxamide with PCl₅ the syntheses of the new N-, C- and pentavalent phosphorus containing heterocycles I and II (see “Inhaltsübersicht”), built up from interconnected four- and fivemembered ring systems, have been achieved. Reaction of N, N′- dimethyloxamide with PCl₃ yields the compound III which may be chlorinated to IV. An intermolecular reaction between the PCl₃- and carbonyl groups of IV gives V. The fivemembered ring systems III and V may each be linked together via N? CH₃ bridges, i. e. via P? N(CH₃)? P and P(O)? N(CH₃)? P(O) units, respectively. N, N′- dimethyloxamide reacts with PCl₅ to form a mixture of fivemembered heterocycles containing trivalent phosphorus (as a PCl group) and chlorinated carbon.     

Phenylphosphonsäure-bis(methylamid) und seine Reaktionen mit Phosphor(III)-Halogeniden

Phenyl Phosphonic Bis(methylamide) and its Reactions with Phosphorus (III) Halides Preparation of phenyl phosphonic bis(methylamide), I , from phenyl phosphonic dichloride and methylamine is described. I is characterized by its nmr, mass, and vibration spectra and by its reactions with PCl₃, CH₃PCl₂, and C₆H₅PCl₂. The two reactions mentioned last yield C₆H₅P(O)[N(CH₃)P(CH₃)Cl]₂ ( IIIa ) and C₆H₅P(O)[N(CH₃)P(C₆H₅)Cl]₂ ( IIIb ), respectively.     

Triorganoantimon- und Triorganobismutdisulfonate Kristall- und Molekülstrukturen von (C6H5)3M(O3SC6H5)2 (M = Sb,Bi)

Triorganoantimony and Triorganobismuth Disulfonates. Crystal and Molecular Structure of (C₆H₅)₃M(O₃SC₆H₅)₂(M = Sb, Bi) Triorganoantimony disulfonates R₃Sb(O₃SR′)₂ [R = CH₃ = Me, C₆H₅ = Ph; R′ = Me, CH₂CH₂OH, Ph, 4-CH₃C₆H₄. R = Ph; R′ = 2,4-(NO₂)₂C₆H₃], Me₃Sb(O₃SCF₃)₂ · 2 H₂O and triphenylbismuth disulfonates Ph₃Bi(O₃SR′)₂ [R = Me, CF₃, CH₂CH₂OH, Ph, 4-CH₃C₆H₄, 2,4-(NO₂)₂C₆H₃] have been prepared by reaction of Me₃Sb(OH)₂, (Ph₃SbO)₂, and Ph₃BiCO₃, respectively, with the appropriate sulfonic acids. From vibrational data an ionic structure is inferred for Me₃Sb(O₃SCF₃)₂ · 2 H₂O and Me₃Sb(O₃SCH₂CH₂OH)₂, and a covalent structure for the other compounds with a penta-coordinated central atom with trigonal bipyramidal surrounding (Ph or Me in equatorial, unidentate sulfonate ligands in apical positions). Ph₃M(O₃SPh)₂ (M = Sb, Bi) crystallize monoclinic [space group P2₁/c; M = Sb/Bi: a = 1 611.5(8)/1 557.4(9), b = 987.5(6)/1 072,5(8), c = 1 859.9(9)/1 696.5(9) pm, β = 105.71(5)/96.62(5)°; Z = 4; d(calc.) 1.556/1.781 Mg · m^?3; V_cell = 2 849.2 · 10⁶/2 814.8 · 10⁶ pm³; structure determination from 3 438/3 078 independent reflexions (I ≥ 3σ(I)), R(unweighted) = 0.030/0.029]. M is bonding to three Ph groups in the equational plane [mean distances Sb/Bi? C:210.1(4)/219.1(7) pm] and two sulfonate ligands with O in apical positions [distances Sb? O: 210.6(3), 212.8(2); Bi? O: 227.6(5), 228.0(4) pm]. Weak interaction of M with a second O atom of one sulfonate ligand is inferred from a rather short M? O contact distance [Sb? O: 327.4(4), Bi? O: 312.9(5) pm], and from the distortion of equatorial angles [C? Sb? C: 128.4(2), 119.2(2), 112.2(2); C? Bi? C: 135.9(3), 117.8(3), 106.3(3)°]     

Reaktionen an Isocyanidverbindungen

By the reaction of FSO₂N?PCl₃ with perfluorpropionic acid FSO₂NHC(O)C₂F₅ is formed, which yields FSO₂N?C(Cl)? C₂F₅ (I) with PCl₅. The chlorine atom in (I) could be replaced by the substituents NH₂ (II) and N(C₂H₅)₂ (III). FSO₂N?C(Cl)? CF₃ reacts with AgOCN, AgSCN, unhydrous HF and 2,3-dimethylbutadiene. FSO₂N(CH₃)? C(O)F reacts with elemental fluorine under exchange of a proton against a fluorine atom to give FSO₂N(CH₂F)? C(O)F, which liberates at room temperature COF₂ and trimerises to form 1,3,5-Tris-fluorosulfonyl-s-triazine (VIII). The amides FSO₂N?C(CH₃)NH₂ and FSO₂N?C(CF₃)NH₂ react with SF₄ in the presence of NaF to yield the iminosulfur difluorides FSO₂N?C(CH₃)? NSF₂ (IX) and FSO₂N?C(CF₃)? NSF₂ (X)     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. III. Die Reaktion zwischen Acrylnitril und PCl3

On Trichlorophosphazo Compounds from Nitriles. III. The Reaction between Acrylonitrile and PCl₃. The reaction of PCl₃ with acrylonitrile at higher temperatures gives CH₂Cl? CCl₂? CCl₂? N? PCl₃ ( II ). On pyrolysis of (II), CH₂Cl? CCl₂? CN (IV) is form- ed. Treatment of (II) with SO, results in CHzCL? CCl₂? CCl?N-P(0)Cl₂ ( III ). At lower temperatures and/or in the presence of PCl₃, acrylonitrile reacts with PCl₃ to give the cis/ trans isomers VIa and VIb .     

Darstellung und Eigenschaften von Tris-(β-chloräthyl) phosphinoxid und Bis-(β-chloräthyl)-(chlormethyl)-phosphinoxid. 43. Mitteilung über organische Phosphorverbindungen [1]

The oxidative degradation of [(HOCH₂CH₂)₃PCH₂OH]⁺Cl^? ( 1 ) with Cl₂ yields, dependent on the pH used, either (HOCH₂CH₂)₃P?O ( 2 ) or (HOCH₂CH₂)₂ (HOCH₂) P?O ( 3 ). Chlorination of 2 and 3 with PCl₅ produces the corresponding chlorides (ClCH₂CH₂)₃P?O ( 4 ) and (ClCH₂CH₂)₂ (ClCH₂)P?O ( 5 ), respectively. Acetylation of 2 and 3 gives the corresponding esters (CH₃CO₂CH₂CH₂)₃P?O ( 6 ), and (CH₃CO₂CH₂CH₂)₂ (CH₃CO₂CH₂)P?O ( 7 ), respectively. Reaction of 7 with HBr results in the formation of (BrCH₂CH₂)₂ (BrCH₂)P?O. Nucleophilic substitution of the chlorine atoms in 4 and 5 with alkoxide or mercaptide gives e.g., 9 , 10 , 11 or 11a , while treatment with tertiary amines yields the vinyl compounds (CH₂?CH)₃P?O ( 12 ) and (CH₂?CH)₂ (CH₂Cl)P?O ( 13 ). 4 and 5 also undergo an Arbuzov type reaction with tertiary phosphites to give 14 and 15 , respectively, which on hydrolysis with conc. HCl give the corresponding acids 16 and 17 , respectively.     

Silicon‐ and Tin‐Containing Open‐Chain and Eight‐Membered‐Ring Compounds as Bicentric Lewis Acids toward Anions

Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me₂Si(CH₂SnMe₂X)₂ ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH₂(SnMe₂CH₂I)₂ ( 7 ), CH₂(SnMe₂CH₂Cl)₂ ( 8 ), cyclo‐Me₂Sn(CH₂SnMe₂CH₂)₂SiMe₂ ( 6 ), cyclo‐(Me₂SnCH₂)₄ ( 9 ), cyclo‐Me_(2?n)X_nSn(CH₂SiMe₂CH₂)₂SnX_nMe_(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt₄[cyclo‐ Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?F] ( 13 ), PPh₄[cyclo‐Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me?Cl] ( 14 ), NEt₄[cyclo‐Me(F)Sn(CH₂SiMe₂CH₂)₂Sn(F)Me?F] ( 15 ), [NEt₄]₂[cyclo‐Cl₂Sn(CH₂SiMe₂CH₂)₂SnCl₂?2 Cl] ( 16 ), M[Me₂Si(CH₂Sn(Cl)Me₂)₂?Cl] ( 17 a , M=PPh₄; 17 b , M=NEt₄), NEt₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?F] ( 18 ), NEt₄[Me₂Si(CH₂Sn(F)Me₂)₂?F] ( 19 ), and PPh₄[Me₂Si(CH₂Sn(Cl)Me₂)₂?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and ¹H, ¹³C, ¹⁹F, ²⁹Si, and ¹¹⁹Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies.     

Untersuchungen über das Reaktionsverhalten von Antimonpentachlorid. III [1]. Zur Reaktion von Antimon (V)-chlorid mit Methylisocyanat

Studies on the Reactivity of Antimony Pentachloride. III. The Reaction of Antimony(V) Chloride and Methylisocyanate Methylisocyanate CH₃NCO reacts with SbCl₅ in boiling CCl₄ by an insertion-reaction to a product of the formula C₅H₆Cl₉N₂O₂Sb I, which has the chlorformamidinium-structure (Cl? C(O)? N(CH₃)? CCl? N(CH₃)? C(O)? Cl)⊕SbCl₆?. Hydrolysis of I yields the heterocycle C₅H₆N₂O₄ II. The reaction with methanol gives (CH₃? NH? CCl? NH? CH₃)⊕SbCl₆? III and (CH₃? NH? CCl? N(CH₃)? C(O)? OCH₃)⊕SbCl₆? IV. The i.r. and Raman spectra of the compounds I, III and IV are discussed.     

Reactions with Oleum under Harsh Conditions: Characterization of the Unique [M(S2O7)3]2− Ions (M=Si,Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag)

The reactions of group 14 tetrachlorides MCl₄ (M=Si, Ge, Sn) with oleum (65 % SO₃) at elevated temperatures lead to the unique complex ions [M(S₂O₇)₃]^2?, which show the central M atoms in coordination with three chelating S₂O₇^2? groups. The mean distances M? O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M? O bonds. For the silicon compound (NH₄)₂[Si(S₂O₇)₃], ²⁹Si solid‐state NMR measurements have been performed, with the results showing a signal at ?215.5 ppm for (NH₄)₂[Si(S₂O₇)₃], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO₆] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S₂O₇)₃]^2? ions is achieved by monovalent A⁺ counter ions (A=NH₄, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A⁺ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S₂O₇)₃]^2? ions remain essentially unaffected with the different A⁺ ions. Furthermore, the nature of the A⁺ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements.     

Reaktionsprodukte aus Chlormethoxiphosphinen und Antimon(V)-chlorid. Schwingungsspektren der 1:1 Addukte aus Methoxiphosphorylverbindungen und Antimon(V)-chlorid

Reaction Products of Chloromethoxiphosphines and Antimony (V) Chloride. Vibrational Spectra of the 1:1-adducts of Methoxiphosphoryl Compounds and Antimony (V) Chloride Chloromethoxiphosphines react with antimony(V) chloride in a redox process to yield the chloromethoxiphospllonium hexachloroantimonates(V) (CH₃O)₃PCl₂⁺SbCl₆^? (II) and CH₃OPCl₃⁺SbCl₆^? (III). II, III, (CH₃O)₃PCl⁺SbCl₆^?(1) and (CH₃O)₄P⁺SbCl₆^? eliminate easily methyl chloride and give the addition compounds OP(OCH₃)₃·SbCl₅(IV), OPCl(OCH₃)₂ · SbCl₅ (V), OPCl₂(OCH₃)·SbCl₅ (VI) and OPCl₃·SbCl₅ (VII). The vibrational spectra of IV, V nnd VI are discussed.