Organische Phosphorverbindungen XXV Darstellung und Eigenschaften von sekundären und tertiären Phosphinsulfiden

Two new processes for the preparation of sec. phosphine sulfides which involve reaction of dialkylamino-dialkyl or diaryl phosphines with hydrogen sulfide, and of dialkylthionophosphonates, (RO)₂P(S)H, with GRIGNARD or organolithium reagents, respectively, are described. The addition of sec. phosphine sulfides to olefins and the condensation of sec. phosphine sulfides with N-hydroxymethyldialkylamines are reported. The conversion of tert. Phosphine sulfides to the corresponding tert. phosphine oxides is readily achieved with hydrogen peroxyde. The physical properties of several new unsymmetrical tert. phosphine sulfide and oxides are listed.     

Darstellung und Struktur von Methylphosphoniumchlorid

Preparation and Structures of Methylphosphonium Chloride The reaction between methyldichlorophosphane and glycol in dichloromethane yields [CH₃PH₃]Cl and CH₂[? OP(O)CH₃(OCH₂CH₂Cl)]₂. The molecular and crystal structure of [CH₃PH₃]Cl are reported.     

Organische Phosphorverbindungen 44 Darstellung und Eigenschaften von Bis-(ß-chloräthyl)-phosphinsäure-Derivaten [1]

Reaction of ClCH₂CH₂PCl₂ with ethylene oxide gives the phosphonous acid ester ClCH₂CH₂P (OCH₂CH₂Cl)₂ which on heating to 120° rearranges to the phosphinic acid ester (ClCH₂CH₂)₂P(O)OCH₂CH₂Cl ( 3 ). Chlorination of 3 with PCl₅ in CCl₄-solution yields the phosphinic chloride (ClCH₂CH₂)P(O)Cl ( 4 ), which on treatment with P₂S₅ at 170° produces the thioderivative, (ClCH₂CH₂)₂P(S)Cl, (₅). Treatment of 4 and 5 with alcohols, mercaptanes, or amines in the presence of an acid binding agent leads to the corresponding phosphinic and thiophosphinic acid derivatives, (ClCH₂CH₂) P (X)Y, (X = O, S; Y = OR, SR, NR₂) ( 6 ). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH₂ = CH)₂P (X) Y (X = O, S; Y = OR, SR, NR₂) ( 7 ). Bis-(ß-chloroethyl)-phosphinates, e. g. (ClCH₂CH₂)₂P (O) OEt, undergo a Michaelis-Arbuzov reaction when heated with phosphites to 160–170° to give bis-(phosphonylethyl)-phosphinates, e.g. (EtO) (O)P[CH₂CH₂CH₂P(O)(OEt)₂]₂ ( 8 ), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO₂P(CH₂CH₂PO₃H₂)₂.     

Zur Darstellung und Struktur von LaTa7O19 Röntgenographische und elektronenmikroskopische Untersuchungen

Preparation and Structure of LaTa₇O₁₉. X-Ray and Electronmicroscopic Investigations In the system La₂O₃/Ta₂O₅ a new ternary compound LaTa₇O₁₉ could be prepared by chemical transport in a temperature gradient T₂ → T₁ (1120 → 1020°C; Cl₂ was added). LaTa₇O₁₉ is hexagonal, space group P6 with the lattice constants a = 6.23₆ and c = 19.99₅ Å. In the structure double layers of pentagonal TaO₇-bipyramids are recognizable perpendicular to [001]-direction. They alternate with a single layer consisting of La? O and Ta? O coordination polyhedra. Images of the structure were made with high resolution transmission electron microscopy along the [001]-direction. Despite the length of the axis the computer simulation based on the multi-slice method agreed well with the experimental images.     

Organische Phosphorverbindungen XXII. Darstellung und Eigenschaften von diprimären α,ω-Bis-phosphino-alkanen

The preparation and properties of diprimary α,ω-bis-phosphino-alkanes of the general structure H₂P(CH₂)_n PH₂ (n = 1, 2, 3, 4) are described. Their reactions with N-hydroxymethyl-dialkylamines and with olefins, which yield ditertiary α,ω-bisphosphino-alkanes, (R₂NCH₂)₂P(CH₂)_nP(CH₂NR₂)₂ and R₂P(CH₂)_nPR₂, respectively, are also reported. The physical properties of two new α,ω-bis-dialkylphosphinyl-alkanes have been determined.     

Zur Darstellung und Struktur von LaTa3O9 Röntgenographische und elektronenmikroskopische Untersuchungen

Preparation and Structure of LaTa₃O₉. X-Ray and Electronmicroscopic Investigations In the system La₂O₃/Ta₂O₅ a new ternary compound LaTa₃O₉ could be prepared by chemical transport in a temperature gradient T₂ → T₁ (1100 → 1040°C; Cl₂ was added). LaTa₃O₉ is orthorhombic, space group Pnma–D with the lattice constants a = 6.59₅, b = 7.66₄, and c = 12.48₁ Å. In the structure ribbons of pentagonal TaO₇-bipyramids are recognizable parallel to the a-direction. These ribbons are connected with each other in the (010) plane by TaO₆-octahedra. The tunnels formed in this way are occupied by La atoms. High resolution transmission electron microscopy images of the structure were made along the [010] direction. They were interpreted by using images calculated on the basis of the multi-slice method.     

Darstellung und Struktur von Li5Ga4

Preparation and Crystal Structure of Li₅Ga₄ Li₅Ga₄ has been established as further, hitherto unknown phase in the LiGa system. The new compound crystallizes in the trigonal system (P3 m1—D_3d³) with a = 437.5 ± 0.2 pm, c = 825.7 ± 0.2 pm, c/a = 1.885. The structure is strongly related to those of LiGa and Li₃Ga₂.     

Organische Phosphorverbindungen 41. Synthese und Eigenschaften von Polyphosphinaten und Polyphosphinsäuren [1]

A process for the preparation of alkyl chloromethylphosphonites, ClCH₂P(OR)₂ (R = Et, Bu), diethyl β-chloroethylphosphonite, ClCH₂CH₂P(OEt)₂, and their conversion to polyphosphinates with the back-bone structures ? [? CH₂PO₂R? ]? _x and ? [? CH₂CH₂P(O₂R)? ]? _x, respectively, by an Arbuzov type reaction is described. Hydrolysis to the corresponding polyphosphinic acids is effected by refluxing the esters with conc. HCl for extended periods. The polyphosphinic acid with structure V is an excellent chelating agent for Ca ions.     

Chromophore in binuklearen ringförmigen Gold(I)-Komplexen

Annular compounds containing two PAuP-entities are prepared by reaction of (trialkylphosphine)gold (I) halogenides with diphosphines. With bis (dimethyl-phosphino)methane (DMPM), 1,2-bis(dimethylphosphino)ethane (DMPE) and 1,3-bis(dimethylphosphino)propane (DMPP) we obtained the following 8-, 10-and 12-membered annular binuclear complexes: [Au(DMPM)]₂Cl₂ H₂O, [Au(DMPM)]₂(SbF₆)₂, [Au(DMPE)]₂Cl₂ 2H₂O, [Au(DMPE)]₂(SbF₆)₂, [Au-(DMPP)]₂Cl₂ and [Au(DMPP)]₂(SbF₆)₂ as identified by conductivity measurements, ¹H- and ³¹P-NMR. spectra and extinction curves. Their absorption spectra differ from those of the isolated linear PAuP-complexes mainly by a very strong band at low energy which is absent in the latter. There is a strong interaction between the PAuP-entities only in certain excited electronic states and an understanding of all transitions is only possible, if both chromophores PAuP and (PAuP)₂ are taken as a basis of interpretation. Bands of the same spectrum belong apparently to two different electronic systems. The absorption spectra of isolated linear and annular ylide-complexes containing one and two CAuC-entities, respectively, show quite the same behaviour.     

Darstellung und Struktur von Pyrazolyl-Kationen mit Polymethin- und Methan-Gerüst

The 4-pyrazoline-3-one1 reacts with 4-dimethylaminobenzaldehyde to yield the stable asymmetric cyanine dye2b which reacts with1 to give the colorless (aryl) (dipyrazolyl) methane3b. Using aldehydes with less cationstabilizing groups the polymethines2 are not isolated but only the methanes3. The structures of2b and3 are discussed by¹ H,¹³C and Hetero NMR spectra.     

Zur Darstellung und Struktur von LaNb5O14

Preparation and Structure of LaNb₅O₁₄ Single crystals of LaNb₅O₁₄ could be prepared by chemical transport reactions (T₂ → T₁; T₂ = 1050°C; T₁ = 950°C) using chlorine as transport agent. LaNb₅O₁₄ crystallizes in the orthorhombic space group Pbem with cell dimensions a = 3.8749(2) Å; b = 12.4407(6) Å and c = 20.2051(9) Å; Z = 4; R = 6.28%, R_w = 3.74%. The structure consists of two types of Nb? O-polyhedra. Especially remarkable are chains of edge-sharing pentagonal NbO₇-bipyramids, which are interconnected by corner-sharing NbO₆-octahedra. Tunnels running in a-direction are created by this framework of NbO₆- and NbO₇-polyhedra. Lanthanum atoms are located in these tunnels at levels inbetween the niobium atoms. The relationship to O? LaTa₃O₉ and M? CeTa₃O₉ type structures will be discussed.     

Darstellung und Struktur von Tetraethylcyclotetraarsoxan-Komplexen von Kupfer(I)-Halogeniden

Preparation and Structure of Tetraethylcyclotetraarsoxane Complexes of Copper(I) Halides The polymeric complexes [Cu₄Cl₄{cyclo-(C₂H₅AsO)₄}₃]_n ( 1 ), [Cu₃Br₃{cyclo-(C₂H₅AsO)₄}₂]_n ( 2 ) and [Cu₆I₆{cyclo-(C₂H₅AsO)₄}₃]_n ( 3 ) were prepared by the reaction of (C₂H₅AsO)_n and CuX (X = Cl, Br, I) in acetonitrile and characterised by X-ray analysis. All three complexes contain only tetramers (C₂H₅AsO)₄ as ligands, in which the As₄O₄ ring systems coordinate between two and four Cu-atoms. In each case one As₄O₄ ring with a crown-shaped conformation is observed, which coordinates either four (in 1 ) or three (in 2 and 3 ) axially sited Cu-atoms. In addition there are further (C₂H₅AsO)₄ ligands, which display either a boat-chair- (in 1 ) or a twist-chair-conformation (in 1–3 ). The individual building units are connected to one another via Cu? X? Cu bridges (in 2 and 3 ) and/or centrosymmetric As₄O₄ ring systems (in 1–3 ) into chain ( 1 ) or layer structures ( 2 und 3 ).     

Organische Phosphorverbindungen XXIII. Sekundäre Phosphinselenide,eine neue Klasse von organischen Phosphorverbindungen

The preparation and properties of secondary phosphine selenides, R₂P(Se)H(R = i-C₄H₉, C₆H₅), a new class of organophosphorus compounds, are described.     

Darstellung,Struktur und Reaktionen von N,N-Difluorsulfonyl-fluoridamid

Preparation, Structure, and Reactions of N,N-Difluorosulfonylfluoridamide FSO₂NF₂ is obtained in high yield by fluorination of FSO₂NH₂ at room temperature. The reaction of FSO₂NF₂ with Et₂NH yields FSO₂NEt₂ and HNF₂. The structure of FSO₂NF₂ was determined by electron diffraction analysis.     

Metallcarbonylkomplexe mit mehrzähnigen ringförmigen Liganden. I. Pentacarbonylkomplexe des s-Trithians und verwandter Verbindungen

Carbonyl Metal Compounds with Polydentate Cyclic Ligands. I. Pentacarbonyl Complexes of s-Trithiane and Related Compounds The complexes (RCHS)_nM(CO)₅ (R = H, CH₃, n = 3; R = H, n = 4; M = Cr^, Mo, W) were prepared from the tetrahydrofuran pentacarbonyl metal compounds and the respective ligands. The Cotton-Kraihanzel force constants of these complexes indicate the sulfur ligands to be slightly more basic than triphenylphosphine. The trimethyltrithiane complexes (R = CH₃, n = 3) exhibit rapid intramolecular exchange of the M(CO)₅-group along the three coordination centers of the ligand.