Schwingungsspektren von Dimethylamino-methoxiphosphorylverbindungen

The Vibrational Spectra of Dimethylamino Methoxiphosphoryl Compounds The vibrational spectra of the known compounds (CH₃O)₂[(CH₃)₂N]PO ( II ), (CH₃O)[(CH₃)₂N]₂PO ( III ), and (CH₃O)[(CH₃)₂N]ClPO ( VI ) are communicated and assigned. The chemical shift of P atoms is listed.     

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.     

Polysulfonylamine. LXXII [1]. Triphenylcarbenium- und Triphenylphosphonium-di(fluorsulfonyl)amid: Zwei Kristallstrukturen mit geordneten (FSO2)2N⊖-Lagen

Polysulfonyl Amines. LXXII. Triphenylcarbenium and Triphenylphosphonium Di(fluorosulfonyl)amides: Two Crystal Structures with Ordered (FSO₂)₂N^? Sites Treatment of HN(SO₂F)₂ in CH₂Cl₂ with Ph₃P, Ph₃PO or collidine (=B) affords the compounds Ph₃PH^⊕[(FSO₂)₂N]^? ( 3 ), Ph₃PO · HN(SO₂F)₂, and BH^⊕[(FSO₂)₂N]^? ( 7 ). The carbenium salt Ph₃C^⊕[(FSO₂)₂N]^? ( 5 ), obtained by metathesis of Ph₃CBr with [(C₆H₆)AgN(SO₂F)₂] in CH₂Cl₂, crystallizes from chloroform/petroleum ether as a monosolvate Ph₃C^⊕[(FSO₂)₂N]^? · CHCl₃ ( 6 ). In presence of a sterically hindered base, viz. collidine, 5 is a suitable reagent for the tritylation of molecules containing weakly activated H atoms (e. g.: MeCN → Ph₃CCH₂CN, acetone → tritylacetone; co-product: 7 ). The crystal structures of the ionic solids 3 (monoclinic, space group P2₁/n) and 6 (monoclinic, P2₁/c) were determined by X-ray diffraction at ?130°C; the structure refinements were not impaired by the notorious tendency of the (FSO₂)₂N moiety towards crystallographic disorder. As in the known structure of the tetraphenylarsonium salt, the anion of 3 and 6 adopts a staggered conformation of approximately C₂ symmetry (averages of all values: S? N? S 121.4°, N? S 156.2, S? O 141.6, S? F 156.6 pm). The crystal packing of 6 displays a three-centre C? H(…?O)₂ hydrogen bond between the CHCl₃ molecule and two oxygen atoms of a single anion, resulting in a six-membered ring [R₁²(6) pattern; H …? O 234 and 262 pm]. The crystal of 3 contains one-dimensional arrays of alternating cations and anions connected by a three-centre P? H(…?O)₂ bond [C(6) pattern; H …? O 237 and 254 pm]. The Ph₃C^⊕ cation of 6 is propeller-shaped, with three coplanar central bonds (mean C? C 144.5 pm) and interplanar angles of 52.7, 56.4 and 60.1° between the phenyl groups.     

Komplexchemie polyfunktioneller Liganden. XXXI. Komplexe des Tetrakis(diphenylphosphorylmethyl)-methan mit FeCl3, SnCl4 und SbCl5

Complex Chemistry of Polyfunctional Ligands. XXXI. Complexes of Tetrakis(diphenylphosphorylmethyl) methane with FeCl₃, SnCl₄, and SbCl₅ C[CH₂P(O)(C₆H₅)₂]₄ forms with FeCl₃ the compounds C[CH₂P(O)(C₆H₅)₂]₄ · 2FeCl₃ and C[CH₂P(O)(C₆H₅)₂]₄ · 4 FeCl₃. From their IR spectra ionic, spirocyclic structures have been derived. C[CH₂P(O)(C₆H₅)₂]₄ yields with SnCl₄ and SbCl₅ also spirocyclic compounds of the composition C[CH₂P(O)(C₆H₅)₂]₄ · 2 SnCl₄ and C[CH₂P(O)(C₆H₅)₂]₄ · 4 SbCl₅, but the SnCl₄ derivative has a nonionic structure.     

l-Hydroxo/Alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimon(V)]Verbindungen. Zweikernige Antimon(V)-Komplexe mit Sulfonatgruppen als überbrückenden Liganden

l-Hydroxo/alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimony(V)] Compounds. Binuclear Antimony(V) Complexes with Sulfonate Groups as bridging Ligands Sulfonic acids react with antimony(V) chloride and water and water/alcohol resp. dependent of the molar ratios yielding Cl₃SbO(OH)(O₂S(O)CH₃)SbCl₃ ( 1 ), Cl₃SbO(OH)· (O₂S(O)CF₃)SbCl₃ ( 3 ) the monohydrate Cl₃SbO(OH)· (O₂S(O)CH₃)SbCl₃·H₂O ( 2 ) and the compounds Cl₃SbO(OR')(O₂S(O)CF₃)SbCl₃ ( 4 : R'=CH₃; 5 : R'=C₂H₅) and Cl₃SbO(OCH₃)(O₂S(O)C₂H₅)SbCl₃ ( 6 ) resp. The crystal and molecular structures of 1 to 3 , 5 and 6 are determined. 1 and 3 are associated by hydrogen bonds to dimers and crystallize monoclinic ( 1 : P2₁/c; 3 : P2₁/n). 2 is a hydroxonium salt H₃O⁺[Cl₃SbO₂(O₂S(O)CH₃)SbCl₃]^– with strong hydrogen bonds between cations and anions and crystallizes triclinic (P1). 5 and 6 crystallize monoclinic ( 5 : P2₁/m; 6 : P2₁/c). In 1 and 3 to 6 there is an intramolecular reorientation or an intermolecular exchange of protons and R' groups in solution. The NMR spectra are discussed.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXIV. Darstellung und Eigenschaften von 3-(N,N-Dialkylamino)-propylmangan-Verbindungen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXIV. Synthesis and Properties of 3-(N,N-dialkylamino)propyl Manganese Compounds MnCl₂ reacts with lithium organyls of the type R₂N(CH₂)₃Li with formation of definite organomanganese complexes. The pure [(CH₃)₂N(CH₂)₃]₂Mn, [(C₂H₅)₂N(CH₂)₃]₂Mn, [(CH₂)₅N(CH₂)₃]₂Mn and the complexes [(CH₃)₂N(CH₂)₃]₂Mn · LiCl and Li{Mn[(CH₂)₃N(CH₃)₂]₃} · 1,5 THF were isolated. [(CH₃)₂N(CH₂)₃]₂Mn · 2 Li(acac) was obtained as a result of reactions of Mn(acac)₂ and Mn(acac)₃ with the corresponding lithium organyl. The σ-organomanganese(II) derivatives were characterized in detail by elementary analysis, molecular weight determination, ESR- and IR-spectra, conductivity measurements and the magnetic moments.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 55. Darstellung und Eigenschaften von Niobocenium- und Tantalocenium-Salzen – Kristall- und Molekülstruktur von [(C5H5)2NbCl2][BF4] · CH3CN

Contributions to the Chemistry of Organo Transition Metal Compounds. 55. Preparation and Properties of Niobocenium and Tantalocenium Salts — Crystal and Molecular Structure of [(C₅H₅)₂NbCl₂][BF₄] · CH₃CN Niobocenium and tantalocenium compounds of the type [(C₅H₅)₂MCl₂]X (X = BF₄, PBh₄, PF₆) were synthesized from the metallocene dichlorides and ferricenium salts, [(C₅H₅)₂Fe]X, in methylene dichloride or tetrahydrofuran. With acetonitrile as solvent [(C₅H₅)₂MCl₂]X · CH₃CN complexes are formed. Stable methyl compounds of the type [(C₅H₅)₂M(CH₃)₂]X were obtained, when (C₅H₅)₂Ta(CH₃)₂ is oxidized by means of ferricenium salts. The new complexes were characterized by elemental analysis, i. r., and ¹H n.m.r. spectra. The structure of [(C₅H₅)₂NbCl₂][BF₄] · CH₃CN has been determined by X-ray structure analysis. The compound crystallizes in the orthorhombic space group Cmcm with a = 8.324(12), b = 19.581(13), c = 9,563(8) Å and Z = 4. The coordination geometry of the Nb atom is tetrahedrally.     

Chlor-dimethylaminosulfonium-Salze Darstellung und IR-Spektren

Chloro-dimethylaminosulfonium Salts. Preparation and I. R. Spectra By reaction of bis-dimethylamino-mono- resp. -disulfane with a mixture of chlorine/antimony(V) chloride the chloro dimethylaminosulfonium hexachloroantimonates(V) [(CH₃)₂N]₂SCI^⊕SbCl₆^? (I) and (CH₃)₂NSCI₂^⊕SbCl₆^? (II) are yielded. The i. r. spectra of these compounds were measured and assigned.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.     

Dihydroxytrimethylstiboran – einige Eigenschaften und Struktur

Dihydroxytrimethylstiborane – Properties and Structure (CH₃)₃Sb(OH)₂ · H₂O ( 1 ) is prepared by reaction of (CH₃)₃SbCl₂ and NaOH. 1 reacts with CO₂ to yield [(CH₃)₃SbOH]₂CO₃ · 2 H₂O ( 2 ). Thermogravimetric investigations and mass spectra show that 1 and 2 decompose at low temperature and low pressure to H₂O, CO₂ and (CH₃)₃SbO. The crystal and molecular structures of 1 and 2 are determined. 1 crystallizes orthorhombic (Pbca) with a = 1185.2, b = 1069.6, c = 1207.6 pm and Z = 8. 2 crystallizes in the acentric monoclinic space group Cc with a = 657.3, b = 1168.5, c = 2048.2 pm, β = 95,33° and Z = 4. The infrared spectra are discussed with regard to the hydrogen bonding.     

Metallorganische Verbindungen mit N-substituierten 3-Hydroxy-2-methyl-4-pyridon-Liganden: quadratisch-planare Rhodium(I)-, Iridium(I)- und Palladium(II)-Komplexe

Organometallic Compounds with N -substituted 3-Hydroxy-2-methyl-4-pyridone Ligands: square planar Rhodium(I), Iridium(I), and Palladium(II) Complexes Reactions of [(OC)₂MCl]₂ (M = Rh, Ir) or [(cod)RhCl]₂ with the anions of N-Aryl or N-Alkyl substituted 3-hydroxy-2-methyl-4-pyridones (O–O′) yield complexes of the general formula [L₂M(O–O′)]. Compounds of this type are also available from reactions of [(OC)₂Rh(acac)] with the corresponding neutral ligands. Substitution of one carbonyl-ligand of the N-phenyl complex [(OC)₂Rh(C₁₂H₁₀NO₂)] ( 2 ) with cyclooctene affords [(OC)(C₈H₁₄)Rh(C₁₂H₁₀NO₂)] ( 8 ). The palladium complexes [(R₃P)Pd(O–O′)Cl] (R = Et, Bu), [(C₆H₄CH₂NMe₂) · Pd(O–O′)] and [(Et₃P)₂Pd(O–O′)]BF₄ ( 9 – 12 ) were synthesized from [(R₃P)PdCl₂]₂, [(C₆H₄CH₂NMe₂)PdCl]₂ or [(Et₃P)PdCl₂]. The structures of the N-methyl compounds [(OC)₂Rh(C₇H₈NO₂)] ( 1 ) and [(Ph₃P)Pd(C₇H₈NO₂)Cl] ( 9 ) were determined by single crystal X-ray diffraction.     

Synthese und strukturelle Charakterisierung von Borsubphthalocyaninaten

Synthesis and Structural Characterization of Boron Subphthalocyaninates Halosubphthalocyaninatoboron, [B(X)_spc] (X = F, Cl, Br) is obtained by heating phthalonitrile with boron trihalide in quinoline (X = F) or the corresponding halobenzene, resp. [B(C₆H₅)_spc] is prepared from phthalonitrile and tetraphenylborate or tetraphenyloboron oxide, resp. [B(OR)_spc] (R = H, CH(CH₃)₂, C(CH₃)₃, C₆H₅) is synthesized by bromide substitution of [B(Br)_spc] in pyridine/HOR. Substitution of [B(Br)_spc] in carboxylic acids yields [B(OOCR)_spc] (R = H, CX₃ (X = H, Cl, F), CH₂X (X = Cl, C₆H₅), C₆H₅). All subphthalocyaninates are characterized electrochemically and by UV‐VIS, IR/FIR, resonance Raman, and ¹H/¹⁰B‐NMR spectroscopy. Typical B–X stretching vibrations are at 622 (X = Br), 950 (Cl), 1063 (F), 1096 cm^–1 (OH) as well as between 1119 and 1052 cm^–1 (OR) resp. 985 and 1028 cm^–1 (OOCR). The difference ν(C=O)–ν(C–O) > 400 cm^–1 confirms the unidentate coordination of the carboxylato ligands. According to the crystal structure analysis of [B(OH)_spc], [B(OH)_spc] · 2 H₂O, [B(C₆H₅)_spc], [B(OC(CH₃)₃)_spc], [B(OOCCH₃)_spc] · 0.5 H₂O · C₂H₅OH and [B(OOCCH₃)_spc] · 0.4 H₂O · 1.1 C₅H₅N the _spc ligand is concavely distorted. This saucer shaped conformation is independent of the acido ligands and the presence of solvate. The outermost C atomes are vertically displaced in part by more than 2 Å from the N_i plane. The B atom is in a distorted tetrahedral coordination geometry. It is displaced by ca 0.64 Å out of the N_i plane towards the acido ligand. The average B–N distance is 1.500 Å, and the B–O distances range from 1.418(5) to 1.473(2) Å.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXVI. Zur Existenz von 3(N,N-Dimethylamino)propyl-Verbindungen der 3d-Elemente und des Zirconiums

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXVI. About the Existence of 3(N, N-Dimethylamino)propyl Compounds of 3d-Metals and Zirconium 3(N, N-dimethylamino)propyl lithium reacts with 3d-metal halides in a different manner. In crystalline state the compounds RTiCl₃, R₃Cr, R₄Zr, and the complexes LiVR₃Cl · 0.7 O(C₂H₅)₂ and Li₂CoR₄ (R = (CH₃)₂NCH₂CH₂CH₂) were isolated. The formation of the unstable R₄Ti and R₂Ni derivatives could be proved. Iron and nickel halides are reduced to the metals by dimethylaminopropyl lithium, even at a temperature of ?60°C.     

Darstellung und Kristallstrukturen von Dipyridiniomethan-Monohalogenohydro-closo-Dodecaboraten(2−), [(C5H5N)2CH2][B12H11X]; X = Cl,Br, I

Preparation and Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Dodecaborates(2?), [(C₅H₅N)₂CH₂][B₁₂H₁₁X]; X = Cl, Br, I [B₁₂H₁₂]^2? reacts with dihalogenomethanes CH₂X₂ in presence of trifluoro acetic acid, yielding the monohalogenododecaborates [B₁₂H₁₁X]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of [(C₅H₅N)₂CH₂][B₁₂H₁₁Cl] · 2(CH₃)₂SO (orthorhombic, space group Pnma, a = 17.351(6), b = 16.034(5), c = 9.659(2) Å, Z = 4) and of the isotypic bromo and iodo compounds [(C₅H₅N)₂CH₂][B₁₂H₁₁X] (monoclinic, space group P2₁/n, Z = 4; for X = Br: a = 7.339(2), b = 15.275(3), c = 16.761(4) Å, β = 96.80(2)°; for X = I: a = 7.4436(8), b = 15.3510(8), c = 16.9213(16) Å, ß = 97.326(7)°) exhibit crystal lattices build up by columns of substituted boron clusters and angular dications [(C₅H₅N)₂CH₂]²⁺ orientated along the shortest axis which are assembled to alternating layers.     

Darstellung und Eigenschaften von Chromorganylen aus Phillips‐Katalysatoren und Ethylen

Surface Compounds of Transition Metals. XLI [1] Preparation and Properties of Organochromium Compounds by Reaction of Phillips Catalysts with Ethylene Reaction of reduced Phillips catalysts with ethylene at 300 °C deactivates the catalyst; supported organochromium compounds are formed. These can be cleaved from the silica support by HCl and other acids, and transferred into solution by extraction with CH₃OH. Chromatography yields fractions of organochromium compounds which differ by CH₂ moieties. XPS, ^1/2H NMR, and mass spectra as well as magnetic measurements prove that an ensemble of (R_nCp)CrCl₂(CH₃OH) (R_nCp = alkylated cyclopentadienyl) has been formed. The R_nCp ligand results from a chromium‐assisted oxidative coupling of the olefin with or without CC‐cleavage. According to UV/Vis and mass spectroscopy Cl^– and CH₃OH can be substituted for other anions and donor molecules. Without a donor dinuclear, Cl‐bridged molecules are obtained, of which [(1,2,3‐Me₃Cp)CrCl₂]₂ was established by crystal structure analysis. Reaction with O₂ reversibly leads to chromium(V) compounds of the type (R₂Cp)Cr(O)Cl₂.     

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimone(V)] Struktur und spektroskopsiche Untersuchungen

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimonies(V)] Structure and Spectroscopic Investigations The title compounds can be prepared by reaction of SbCl₅ · H₂O and RCOOH (R ? CF₃, CCl₃, CHCl₂, CH₂Cl, CH₃, CH₃CH₂, (CH₃)₂CH, H) or by reaction of H₅O₂⁺SbCl₆^? and RCO₂SbCl₄ in good yields. ¹H-NMR investigations proove that there is a rapid exchange between the components in the reaction mixture. The vibrational spectra are discussed in view of the CO₂ vibrations and hydrogen bonding. The crystal and molecular structure of dh-μ-Trichloroacetato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimony(V)] is determined by X-ray analysis.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.     

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.     

Übergangsmetall-carben-Komplexe. LXXX. α-Alkoxy- und α,α-dialkoxysubstituierte Phenylacetyl-(pentacarbonyl)metallate und Pentacarbonyl[alkoxy(benzyl)-carben]-Komplexe des Chroms und Wolframs

Vibrational Spectra of Dichlorophosphorylmethylamine CH₃? NH? P(?O)Cl₂ and its Adducts with SbCl₅ and SnCl₄ The vibrational spectra of liquid samples and solutions, as well as cryoscopic molecular weight determinations show that CH₃? NH? P(?O)Cl₂ exists largely in the dimeric form. The association occurs through hydrogen bridges. The adducts SbCl₅ · CH₃? NH? P(?O)Cl₂ and SnCl₄ · 2 CH₃? NH? P(?O)Cl₂ are formed through addition via an oxygen atom. The ligands have cis-configuration in the tin compound.     

Synthese linearer und verzweigter Phosphazene aus N-silylierten Phosphorylamiden

Synthesis of Lineary and Branched Phosphazenes from N-silylated Phosphoryl Amides The use of N-silylated phosphoryl amides in the reaction with PCl₅ favours the KIRSANOV reaction and reduces undesirable substitution reactions. However, silylated monoamides, X₂P(O)NHSiMe₃ (X = OEt, NEt₂), do not give the expected trichlorophosphazenes but the isomeric N-dichlorophosphoryl phosphazenes, Cl₂P(O)? N?PClX₂, which are also formed in the reaction of (EtO)₂P(O)NCl₂ with PCl₅. As the first phosphoryl-P, P-bis(trichlorophosphazene) (EtO)P(O)(N?PCl₃)₂ could be obtained in the reaction of PCl₅ with the silylated diamide (EtO)P(O)(NHSiMe₃)₂. Tris reactivity of silylated amides to P? Cl compounds decreases in the row PCl₅ > POCl₃ > CIP(O)(OEt)₂ > ClP(O)(NEt₂)₂. In the reaction with phosphoryl chlorides the preferred formation of compounds with P? NH? P bridges could not be observed.