Synthese und Strukturbestimmung von (i-Pr)2NB(t-BuP)3 und (i-Pr)2NB(t-BuP)4

Synthesis and Structure Analysis of (i-Pr)₂NB(t-BuP)₃ and (i-Pr)₂NB(t-BuP)₄ The diphosphide K(t-Bu)P-(t-BuP)₂-P(t-Bu)K obtained by the cleavage reaction of the 3-membered ring system (i-Pr)₂BN(t-BuP)₂ with potassium reacts with t-BuPCl₂ at ?78°C under ring expansion to form the P₃B ring system (i-Pr)₂NB(t-BuP)₃ – 1,2,3-tri-t-butyl-tri-phospha-4-diisopropyl-aminoboretane ( 1 ). – The 5-membered P₄B ring system (i-Pr)₂NB(t-BuP)₄ – 1,2,3,4-tetra-t-butyl-tetraphospha-5-diisopropylaminoborolidine, ( 2 ) – is formed from K(t-Bu)P? (t-BuP)₂? P(t-Bu)K and (i-Pr)₂NBCl₂ analogous to the above reaction. 1 and 2 could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analysis. 1 shows at 200 K two conformation isomers; for 2 ³¹P-^10,11B-isotopic shifts could be identified.     

Synthese,Charakterisierung und Struktur von P7(t-Bu3Si)3 („Tris(supersilyl)heptaphosphan(3)”︁)

Synthesis, Characterization, and Structure of P₇(t-Bu₃Si)₃ (?Tris(supersilyl)heptaphosphane(3)”? Tris(tri-tert-butylsilyl)heptaphosphanortricyclane P₇(t-Bu₃Si)₃ 1 is obtained from the reaction of (t-Bu)₃Si? Si(t-Bu)₃ with white phosphorus and forms colorless to pale yellow thermostable crystals. 1 is identified by the complete analysis of its ³¹P{¹H} NMR spectrum (A[MX]₃ spin system) as well as by a single crystal structure determination (space group Pca2₁, a = 170.76(2)pm, b = 131.14(3)pm, c = 426.61(5)pm, α = β = γ= 90°, Z = 8 formula units in the elementary cell). The steric demand of the (t-Bu)₃Si-Groups causes an increase of the exocyclic bond angles at the equatorial phosphorus atoms P^e, while it does not particularly influence the P₇-skeleton. Chlorine (r.t.) and bromine (70°C) degrade the P₇-cage of 1 with formation of PX₃ and (t-Bu)₃SiX (X = Cl, Br).     

[t-Bu2P]3P7 und (t-Bu2Sb)3P7 sowie Untersuchungen zur Bildung von Heptaphosphanen(3) mit PMe2-, PF2- und P(CF3)2-Gruppen

[t-Bu₂P]₃P₇ and (t-Bu₂Sb)₃P₇, as well as Investigations on the Formation of Heptaphosphanes (3) Containing PMe₂, PF₂, and P(CF₃)₂ Groups Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu₂P)₃P₇ 1 obtained by reacting Li₃P₇ · 3 DME with t-Bu₂PF forms yellow crystals. (t-Bu₂Sb)₃P₇ 2 produced similarly from t-Bu₂SbCl and Li₃P₇ · 3 DME didn't form crystals; it decomposes in a solution of toluene above ?10°C. Both compounds were identified by their ³¹P{¹H} NMR spectra, and 1 also by elemental analysis and single crystal structure determination (space group) P2₁/a, a = 1 712.0(9) pm, b = 1 105.1(7) pm, c = 1 854.0(10) pm, β = 94.96(4)°, Z = 4 formula units in the elementary cell). Attempts to synthesize (Me₂P)₃P₇ 3 , (F₂P)₃P₇ 4 and [(F₃C)₂P]₃P₇ 5 failed as dialkylchlorophosphanes as Me₂PCl e. g. with Li₃P₇ · 3 DME react under Li/Cl exchange, dialkylfluorophosphanes (except t-Bu₂PF) disproportionate, and neither PF₃ nor (F₃C)₂PBr with Li₃P₇ · 3 DME give the desired products 4 or 5 , resp.     

Die CuCl-katalysierte Reaktion von Trimethylsilyl(t-butyl)chlorphosphan mit Dimethylzirconocen: Ein Beispiel der Tandem-Katalyse

The CuCl-catalyzed Reaction of Trimethylsilyl(t-butyl)chlorophosphane with Dimethylzirconocene: An Example for Tandem Catalysis t-BuP(SiMe₃)Cl was prepared from t-BuP(SiMe₃)₂ and hexachloroethane and reacted in situ with Cp₂ZrMe₂ in the presence of catalytic amounts of copper(I) chloride yielding t-Bu(Me)P? P(Cl)t-Bu ( 1 ) (2 : 1 reaction) or t-Bu(Me)P? P · (Me)t-Bu ( 2 ) (1 : 1 reaction) and Cp₂ZrCl(Me). To understand the course of reaction, the reaction of dimethylzirconocene with CuCl and the decomposition of t-BuP(SiMe₃)Cl in the presence of CuCl and tetrachloroethene were studied. The results suggest that CuCl reacts with t-BuP(SiMe₃)Cl in the presence of C₂Cl₄ to give t-Bu(Cl)P? P(Cl)t-Bu ( 3 ); simultaneously, CuCl reacts with Cp₂ZrMe₂ with formation of methylcopper, which reacts with 3 to give 1 or 2 , respectively.     

Reaktionen von Tetraphosphortrichalkogeniden mit Alkyliodiden

Reactions of Tetraphosphorus Trichalcogenides with Alkyl Iodides Reactions of alkyl iodides RI (R = CHI₂, CH₂I or tert-Butyl) with P₄E₃ (E = S or Se) under the influence of light resulted in cleavage of the basal P₃ ring. β-P₄E₃(I)R was formed initially, then it rearranged to the more stable α-P₄E₃(I)R structure. ³¹P NMR data of these products were measured and discussed, along with ⁷⁷Se data for α- and β-P₄⁷⁷SeSe₂(I)CHI₂. On reaction of P₄S₃ with tert-butyl iodide in CS₂ or with sec-butyl iodide or iso-propyl iodide in dioxane, the new type of compounds P₅S₂R was observed. In this a sulfur bridge of P₄S₃ is replaced by a P? R group. ³¹P-NMR data for these compounds are reported.     

Synthesis,crystal structure,magnetism and vibrational spectrum of Dipotassium Iron(II) Hexathiodiphosphate(IV), K2Fe[P2S6]

K₂Fe[P₂S₆] was synthesized from the elements at 1173 K in sealed quartz tubes. The compound forms transparent orange crystals, stable against air and moisture. K₂Fe[P₂S₆] crystallizes in the monoclinic system, space group P2₁/n (No. 14), with cell dimensions (T = 298.5 K) a = 6.0622(4), b = 12.172(1) and c = 7.3787(8) Å, β = 101.113(7)°, Z = 2. The novel structure type (mP22) is characterized by columns of alternating face-sharing S₆ octahedra and trigonal antiprisms (both distorted) parallel to the a axis, which are interconnected by inserted K⁺ (CN 10; {2,6,2}-polyhedra; d(K? S) = 3.231 ? 3.845 Å). The S₆ polyhedra of the columns are centered alternately by Fe (d?(Fe? S) = 2.577 Å) and P₂ pairs which are inclined to the a axis by 73.4°. The bond lengths in the hexathiodiphosphate(IV) anions, [P₂S₆]^4?, with approximate 3 2/m – D_3d symmetry, are d?(P? P) = 2.20 and d?(P? S) = 2.02 Å. The compound is paramagnetic above T_N = 28 K with μ = 4.69 B.M. and orders antiferromagnetically below T_N. The internal modes of the observed Raman and FIR spectra of K₂Fe[P₂S₆] are in accord with the factor group analysis, and the spectra are assigned on the basis of [P₂S₆]^4? units, taking into account the deviation from D_3d symmetry.     

Komplexchemie P-reicher Phosphane und Silylphosphane. VII. Carbonylkomplexe des Heptaphosphans(3) iPr2(Me3Si)P7

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII Carbonyl Complexes of the Heptaphosphane(3) iPr₂(Me₃Si)P₇ From the reaction of iPr₂(Me₃Si)P₇ 1 with one equivalent of Cr(CO)₅THF the yellow products iPr₂(H)P₇[Cr(CO)₅] 2 and iPr₂(Me₃Si)P₇[Cr(CO)₅] 3 were isolated by column chromatography on silicagel. The P? H group in 2 results from a cleavage of the P? SiMe₃ bond during chromatography. The Cr(CO)₅ group in 2 is linked to an iPr? P^e atom, in 3 to the Me₃Si? P^e atom of the P₇ skeleton. The substituents do not force the formation of a single isomer; nevertheless 3 ist considerably favoured as compared to 2 . From the reaction of 1 with 2 equivalents of Cr(CO)₅THF the yellow iPr₂(H)P₇[Cr(CO)₅]₂ 4 was isolated bearing one Cr(CO)₅ group at an iPr? P^e atom, the other one at a P^b atom of the P₇ skeleton. Compound 3 yields with Cr(CO)₄NBD the red iPr₂(Me₃Si)P₇[Cr(CO)₅][Cr(CO)₄] 5 . Three isomers of 5 appear. Two P^e atoms of 5 are bridged by the Cr(CO)₄ group, the third P^e atom is linked to the Cr(CO)₅ ligand. iPr₂(H)P₇[Fe(CO)₄] was isolated from the reaction of 1 with Fe₂(CO)₉. ³¹P NMR and MS data are reported.     

Über die Umsetzung von P4E3I2 (E = S,Se) mit einigen Carbonsäuren und Dithiocarbonsäuren

On the Reaction of P₄E₃I₂ (E = S, Se) with some Carboxylic Acids and Dithiocarbamic Acids By the reaction of α-P₄E₃I₂ (E = S, Se) with carboxylic acids, dithiobenzoic acid or dithiocarbamic acids in the presence of triethylamin or with (C₆H₅)₃SnR, or of β-P₄E₃I₂ with tin-organic compounds α-P₄E₃(I)R, α(β)-P₄E₃R₂ [R = ? OC(O)C₆H₅, ? OC(O)CH₃, ? SC(S)NC₅H₁₀, ? SC(S)N(C₂H₅)₂], α-P₄S₃(I)SC(S)C₆H₅, α-P₄S₃(SC(S)C₆H₅)₂ and β-P₄E₃(I)R (R = ? OC(O)C₆H₅, ? OC(O)CH₃) were prepared in solution and identified by ³¹P NMR spectroscopy. In addition α-P₄S₃(NC₅H₁₀)(SC(S)NC₅H₁₀) was detected. The β-isomers could be obtained also with lesser yields by the reaction with the dithiocarbamic acids, too. The substitution of the second iodine ligand in β-P₄E₃I₂ resulted mainly in β-P₄S₃(R_exo)₂ and by inversion of the configuration at a phosphorus atom, in β-P₄E₃R_exoR_endo. α-P₄S₃I₂ reacted with methanol in CS₂ to α-P₄S₃(OCH₃)(SC(S)OCH₃) and α-P₄S₃(SC(S)OCH₃)₂. The ³¹P NMR data of the compounds are discussed. The ³¹P NMR spectra of the α(β)-P₄E₃ dithiocarbamates indicate dynamic processes in the solution, e. g. α-P₄S₃(I)(SC(S)NR₂) showed an intramolecular conversion, due to the anisobidentate dithiocarbamate ligand. This behaviour had not previously been noticed for compounds with a P₄S₃-skeleton.     

Crystal Structure and Vibrational Spectrum of Dipotassium Manganese(II) Hexathiodiphosphate(IV), K2Mn[P2S6]

K₂Mn[P₂S₆] was synthesized from the elements in sealed quartz ampoules at 1 173 K. The compound forms transparent light brown crystals, stable against air and moisture. The crystal structure (monoclinic; space group P2₁/n, No. 14; a = 6.1966(9), b = 12.133(2), c = 7.424(1) Å, β = 101.52(1)°, Z = 2; Pearson code mP22) consists of columns of face-sharing S₆ polyhedra (distorted octahedra and trigonal antiprisms) parallel to the a axis, interconnected by inserted K⁺ (CN 10; d(K? S) = 3.23–3.92 Å). The S₆ polyhedra of the columns are centered alternately by Mn (in octahedra with d?(Mn? S) = 2.647 Å) and P₂ pairs (in trigonal antiprisms) which are inclined to the a axis by 73.1°. The bond lengths in the resulting hexathiodiphosphate(IV) anions, [P₂S₆]^4?, with approximate 3 2/m–D_3d symmetry, are d(P? P) = 2.211 Å and d(P? S) = 2.018 Å. K₂Mn[P₂S₆] is isotypic to K₂Fe[P₂S₆], being the second member of this structure type. The internal modes of the observed Raman and FIR/IR spectra of K₂Mn[P₂S₆] are in accord with the factor group analysis, and the fundamentals are assigned on the basis of [P₂S₆]^4? units, taking into account the deviation of the D_3d symmetry.     

Synthese und Struktur von Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octan – Eine neue Käfigverbindung mit dem Sn(P2)3Sn-Gerüst

Synthesis and Structure of Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane – a New Cage Compound with the Sn(P₂)₃Sn Skeleton The reaction of the diphosphide K₂[(tBuP)₂] 1 with SnCl₄ leads by a redox process mainly to (tBuP)_3,4 and other sideproducts. However, at the same time a threefold [2 + 1]-cyclocondensation reaction takes place yielding the new cage compound hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane, ClSn(tBuP? PtBu)₃SnCl 2 . 2 could be obtained in a pure form and characterized ³¹P and ¹¹⁹Sn NMR spectroscopically; 2 was also characterized by a single crystal structure analysis.     

C–Gd2S3 und C–Tb2S3: Darstellung und Röntgenstrukturanalyse von Einkristallen

C–Gd₂S₃ and C–Tb₂S₃: Synthesis and X-Ray Structure Analysis of Single Crystals Pale yellow, bead-shaped single crystals of C-type Gd₂S₃ (a = 838.47(9) pm) and Tb₂S₃ (a = 835.23(9) pm) are obtained upon the oxidation of the respective rare-earth metal (M = Gd and Tb) with sulfur (molar ratio 2 : 3) in evacuated silica tubing at 700 °C in the presence of fluxing CsCl within five days. Their crystal structure belongs to a cation-deficient Th₃P₄-type variant (cubic, I43d) according to M_2.667□_0.333S₄ (Z = 4) or M₂S₃ (Z = 5.333) offering coordination numbers of eight (S^2– arranged as trigonal dodecahedra) to the cations. In spite of the high Cs⁺ activity in molten CsCl, no cesium incorporation into the M_5.333□_0.667S₈-frame structure (e. g. as CsM₅S₈ with Z = 2) can be achieved, judged from refined occupation factors of M³⁺ very close to x = 8/9 for M_3xS₄.     

Komplexchemie at P-reicher Phosphane und Silylphosphane. VI. Bildung und Struktur der Chromcarbonylkomplexe des Tris(trimethylsilyl) heptaphosphanortricyclans (Me3Si)3P7

Formation and Structures of Chromium Carbonyl Complexes of Tris(trimethylsily)heptanortricyclane (Me₃Si)₃P₇ (Me₃Si)₃P₇ 1 reacts with one equivalent of Cr(Co)₅THF 2 to give the yellow (Me₃Si)₃P₇[Cr(Co)₅] 4. The Cr(Co)₅group is attached to a P^e atom. Yellow (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 is obtained either from reacting 1 with two equivalents of 2 , or from 4 with one equivalent of 2. One Cr(CO)₅ groups in 5 is coordinated to a P^e atom, the other one to a P,^b atom. Similarly, Yellow (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 results from reacting 5 with one equivalent of 2 . Two Cr(CO)₅ groups in 6 are linked to P^b atoms, and the third one either to a P^e or the P^a atom (assignment not completely clear). Derivatives containing a P^e bridge appear in reactions of 1 with higher amounts of 2 . Such, 5 forms mixtures of the red compounds (Me₃Si)₃P₇ × [Cr(CO)₅]₂[Cr(CO)₄] 8 and (Me₃Si)₃P₇[Cr(CO)₅] × [Cr(CO)₄] 9 , and even preferably 9 with four equivalents of 2 . In 8 , one Cr(CO)₅ group is attached to that p^e atom which is not engaged in the Cr(CO)₄ bridge, and the second to one of the P^b atoms directly adjacent to the bridge. The additional Cr(CO)₅ group in 9 is coordinated to the remaining P^b atom directly adjacent to the bridge. In reactions of 5 with even higher amounts of 2 , four Cr(CO)₅ groups and one Cr(CO)₄ bridge attach to the basic P₇ skeleton to from the less stable Me₃P₇[Cr(CO)₅]₄[Cr(CO)₄]. (Me₃Si)₃P₇ 1 reacts considerably slower with Cr(CO)₅THF 2 than R₃P₇ (R = Et, iPr). Cr(CO)₄NBD 3 reacts with 1 , but it was not possible to isolate (Me₃Si)₃P₇[Cr(CO)₄]. However, 4 with 3 forms (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 , and 5 with 3 yields (Me₃Si)₃P₇[Cr(CO)₅]₂[Cr(CO)₄] 8 . The structures of 4 , 5 , 7 , 8 or 9 are quite analogous to those of the derivatives of Et₃P₇ but there exist significant differences in stability and reactivity. While Et₃P₇[Cr(CO)₅]₂ in solution rearranges to give the stable Et₃P₇[Cr(CO)₅][Cr(CO)₄], the analogous (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 is not stable and is not obtained from (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 . Et₃P₇[Cr(CO)5]₃ can just be detected spectroscopically and rearranges easily to give Et₃P₇[Cr(CO)₅]₂ [Cr(CO)₄] whereas (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 can be isolated. These differences are caused by the greater steric requirements of Me₃Si groups. The formation of a P^e–Cr(CO)₄–P^e bridge, e.g., requires a Me₃Si group in 1 to switch from the s to the as position. Whereas many of the complex compounds of R₃P₇ (R = Et, iPr) crystallize easily, the analogous derivatives of (Me₃Si)₃P₇ did not yield crystals. The structures of the products were assigned by evaluating the coordination shift in their ₃₁P NMR spectra and by comparision of these spectra with those of such derivatives of Et₃P₇ which previously had been investigated by single crystal structure determinations.     

The Preparation and X-Ray Structure of [AsPh4][Ph2P(S)NSiMe3] · 0.5 THF

The reaction of Ph₂P(S)N(SiMe₃)₂ with potassium tert-butoxide in a 1:1 molar ratio produces K[Ph₂P(S)NSiMe₃], which was converted to the AsPh₄⁺ salt by metathesis with [AsPh₄]Cl. The X-ray crystal structure of [AsPh₄][Ph₂P(S)NSiMe₃] · 0.5 THF consists of noninteracting AsPh₄⁺ and Ph₂P(S)NSiMe₃^? ions with d(P? S) = 1.980(4) Å and d(P? N) = 1.555(8) Å. The PNSi bite angle in the anion is 136.3(5)°. Electrophilic attack by Ph₂P(S)Cl occurs at the sulfur atom of Ph₂P(S)NSiMe₃^?. The oxidation of the anion with iodine produces a disulfide which regenerates K[Ph₂P(S)NSiMe₂] upon treatment with potassium tert-butoxide.     

Kristallstruktur und Eigenschaften von Calcium- und Strontiumhexathiodiphosphat(IV), Ca2P2S6 und Sr2P2S6, mit einem Beitrag zu Ca5P8 und Pb2P2S6

Crystal Structure and Properties of Calcium and Strontium Hexathiodiphosphate(IV), Ca₂P₂S₆ and Sr₂P₂S₆, with a Contribution on Ca₅P₈ and Pb₂P₂S₆ Ca₂P₂S₆ and Sr₂P₂S₆ were prepared from metal and a mixture of red phosphorus and sulfur (molar ratio M:P:S = 1:1:3) in 2 corundum crucibles inserted in quartz ampullae under vacuum (20 d 900°C). The compounds were obtained as colourless, crystalline powders containing single crystals. They crystallize in the Sn₂P₂S₆ (high temperature form) type structure (P2₁/c, Z = 2): Ca₂P₂S₆ a = 653.2(2)pm, b = 728.1(2)pm, c = 1110.1(4)pm, β = 124.00(4)°, d = 2.50(2); Sr₂P₂S₆ a = 664.3(2)pm, b = 755.7(3)pm, c = 1139.7(3)pm, β = 124.07(2)°, d = 2.97(2). The anions P₂S have staggered confirmation and are arranged with the motif of a cubic close-packing. Sr²⁺ is coordinated by 8S which form a twofold face-capped trigonal prism and belong to 4P₂S. Structure calculations clearly show that Pb₂P₂S₆ also crystallizes in P2₁/c and not in Pc [1]. Also, Raman- and IR-spectra of Ca₅P₈ were recorded at 20°C. The stretching vibrations of P were assigned in analogy to those of P₂S in alkaline earth hexathiodiphosphates(IV). The range of their frequencies (480 to 340 cm^?1) is essentially smaller and shifted to smaller values compared with P₂S in Ca₂P₂S₆ and Sr₂P₂S₆ (620 to 390 cm^?1). The symmetry of P is not D_3d but C_2h as in the case of P₂S.     

Synthesis of well‐defined second‐generation dendritic polymers of isoprene (I) and styrene (S): (S2I)3, (SI′I)3, (I″I′I)3, and (I′2I)4

The synthesis of second‐generation (G‐2) dendritic polymers of isoprene (I) and styrene (S) was achieved with anionic polymerization high‐vacuum techniques and by performing the following steps: (1) selective reaction of a living chain with the chlorosilane group of 4‐(chlorodimethylsilyl)styrene (a dual‐functionality compound) to produce a macromonomer, (2) addition of a second living chain (same or different) to the double bond of the macromonomer, (3) polymerization of I with the anionic sites, and (4) reaction of the produced off‐center living species with trichloromethyl silane or tetrachlorosilane (CH₃SiCl₃ or SiCl₄). The combined characterization results showed that the G‐2 dendritic macromolecules synthesized—(S₂I)₃, (SI′I)₃, (I″I′I)₃, (I′₂I)₄—have a high molecular and compositional homogeneity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1519–1526, 2002     

(S)-6-苄氧基-5-羟基-3-氧代-己酸叔丁酯合成新方法

研究了一条新的路线用于(S)-6-苄氧基-5-羟基-3-氧代-己酸叔丁酯的合成. 以廉价、易得的R-环氧氯丙烷为起始原料, 经过几步比较温和的反应得到目标化合物. 在此基础上, 通过对催化剂三氟化硼乙醚用量的考察以及两条反应路线优缺点的比较, 找到了一条适合大规模制备的工艺路线. 该路线具有收率高、原料易得、反应条件温和、产物容易分离、提纯等特点.     

Zur Chemie von Sulfiden und Seleniden primärer Phosphane — Die (1-Hydroxyalkyl)-organyl-phosphansulfide und -selenide,neue Verbindungsklassen

Investigation into Sulfides and Selenides of Primary Phosphines — The (1-Hydroxyalkyl)-organyl-phosphine Sulfides and Selenides, New Classes of Compounds Primary phosphines react with S₈ and Se₈, respectively, forming organylphosphine monosulfides, and monoselenides, respectively, RP(X)H₂ (X = S, Se) which are well characterized by ³¹P NMR spectroscopy. Organylphosphine monosulfides are detected in the reaction mixture of primary phosphines with 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides, too. The reaction of primary phosphines with sulfur or selenium proceeds in presence of most of the ketones without formation of any side product. The (1-hydroxyalkyl)-organyl-phosphine sulfides and selenides, respectively, RP(X)(H)C(OH)R¹R², are yielded generally in crystalline form. The X-ray crystal structure analysis of the (1-hydroxy-1-methyl-ethyl)-phenyl-phosphane sulfide (R = Ph, R¹ = R² = Me) has shown that in the crystal the molecules are chained via intermolecular O? H …? S hydrogen bridging bonds (O …? S = 328 pm). Aldehydes react with primary phosphines and sulfur forming bis(1-hydroxyalkyl)-phenyl-phosphine sulfides, RP(S)[CH(OH)R¹]₂. ¹H, ¹³C, and ³¹P NMR spectroscopic investigations allow to detect and to identify stereoisomers in some cases. Quantumchemical calculations reflect correctly which of the carbonyl compounds are able to react with the organylphosphine monosulfide formed as intermediate.     

Synthesis and Characterization of Copper Hexathiometadiphosphate Cu2P2S6

Copper hexathiometadiphosphate, Cu₂P₂S₆, was synthesized and characterized. Brick‐red copper hexathiometadiphosphate Cu₂P₂S₆ crystallizes in the tetragonal space group P4₂/mnm (no. 136) with a = b = 5.2565(7), c = 15.066(3) Å and V = 416.3(1) ų in a novel structure type. This is the first hexathiometadiphosphate, whose crystal structure is based on a slightly distorted cubic closest packing of sulfur atoms. 1/3 of the tetrahedral voids are occupied by Cu and P in an ordered fashion, thus resulting in a layered structure. The structural motif of layers composed of corner‐sharing CuS₄ tetrahedra (comparable to red HgI₂) that are separated by [P₂S₆]^2– anions orientated perpendicular to these layers, is rarely found in solid state chemistry. The compound is diamagnetic and shows negligible electronic conductivity. Electronic structure calculations and UV/Vis measurements point to a bandgap in the visible range and explain the red color of the compound. Additionally, the oxidation state +1 for Cu was confirmed by the electronic structure calculations. The thermal properties of Cu₂P₂S₆ were investigated by DTA.     

Reaction of [P3N3Cl4(NH2)2] with [HN(POCl2)2]; The crystal structure of the phosphazenium salt [P3N3HCl4(NH2)2]+[N(POCl2)2]−

The reaction of diaminotetrachloro-cyclotriphosphazene with tetrachloride of μ-imino-diphosphoric acid leads to the formation of the salt-like compound [P₃N₃HCl₄(NH₂)₂]⁺[N(POCl₂)₂]⁻ which identity was unambiguously established by means of X-ray structure analysis. The structure is composed of [P₃N₃HCl₄(NH₂)₂]⁺ cations and [N(POCl₂)₂]⁻ anions joined by a system of H-bonds. As in other phosphazenium salts, the protonation of the ring N atom leads to significant changes in the endocyclic P N bond lengths.     

Zur Chemie und Strukturchemie von Phosphiden und Polyphosphiden. 581) Tetrabariumtriphosphid,Ba4P3: Darstellung und Kristallstruktur

Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 58. Tetrabariumtriphosphide, Ba₄P₃: Preparation and Crystal Structure Ba₄P₃ is obtained from the elements in the molar ratio 4:3 or by reaction of Ba₃P₂ and Ba₅P₄ in the molar ratio 1:1 (steel ampoules with inner corundum crucibles; 1 490 K). The greyish black, easily hydrolysing compound crystallizes in a new structure type oP56. The structure shows two crystallographically independent dumbbells P₂^4? (d(P? P) = 225 and 232 pm) and isolated ions P^3? corresponding to (Ba²⁺)₈(P₂^4?)₄(P^3?)₄. The partial structure of the Ba atoms forms a complex network of trigonal prisms with tetrahedral and square pyramidal holes, as well as polyhedra with 14 faces (CN 10) which are icosahedron derivatives. The P^3? anions center trigonal prisms and the 14 face polyhedron. The P-atoms of the P₂^4? dumbbells center neighboring trigonal prisms with common square faces. (Pbam (no. 55); a = 1 325.4(2) pm, b = 1 256.2(2) pm, c = 1 127.3 pm; Z = 8).