Beiträge zur Chemie des Phosphors. 151. Dilithium-dihydrogentetradecaphosphid,Li2H2P14: Darstellung und strukturelle Charakterisierung

Contributions to the Chemistry of Phosphorus. 151. Dilithium Dihydrogen Tetradecaphosphide, Li₂H₂P₁₄: Preparation and Structural Characterization Dilithium dihydrogentetradecaphosphide, Li₂H₂P₁₄ ( 1 ), is obtained as an orange-red solvent adduct Li₂H₂P₁₄ · 6 THF in a purity of 80–90 per cent by reacting P₂H₄ with n-BuLi under suitable conditions. 1 is also formed in the reaction of Li₃P₇ or LiH₄P₅ with P₂H₄, and in the disproportionation of LiH₄P₇. According to its 2D-³¹P-NMR spectrum 1 is a conjuncto-phosphane built up by one P₇(5)^?- and one P₉(3)^?-unit group with structures analogous to norbornane and delta-cyclane, respectively.     

Beiträge zur Chemie des Phosphors, 45. Triphenyl-cyclotriphosphan - ein Derivat des P3H3

Contributions on the chemistry of phosphorus. 45. Triphenyl cyclotriphosphane - a derivative of P₃H₃ Triphenyl-cyclotriphosphane-dipotassium ( 2 ) can be prepared without solvent by metallation of pentaphenyl-cyclopentaphosphane ( 3 ) with the stoichiometric amount of potassium in benzene, moreover by precipitation of the corresponding reaction solution in tetrahydrofuran with toluene or petroleum ether. However, 2 · THF is formed when the solvent is removed completely, 2 or 2 · THF react with iodine at - 78°C to give the compounds K₂(C₆H₅P)₃ (4) or 4 · THF. These decompose in solution under formation of potassium iodide and triphenyl-cyclotriphosphane ( 1 ), not described before. 1 could be isolated in a pure state. It differs from 3 by its characteristic melting behaviour and the osmometric molecular weight, but especially by the i.r. and mass spectrum. 1 is stable at ? 20 °C for several weeks, but rearranges easily to give the more stable 3 , especially at somewhat higher temperatures.     

Beiträge zur Chemie des Phosphors. 200. Tetraisopropyl-tetradecaphosphan(4), P14(i-Pr)4 – Darstellung und strukturelle Charakterisierung

Contributions to the Chemistry of Phosphorus. 200. Tetraisopropyl-tetradecaphosphane(4), P₁₄(i-Pr)₄ – Preparation and Structural Characterization Tetraisopropyl-tetradecaphosphane(4) ( 1 ) has been obtained by reacting i-PrPCl₂, P₄, and magnesium and subsequently thermolysing the crude reaction product, and has been isolated in pure form. Whereas the ³¹P{¹H}-NMR spectrum provides only limited structural information, the ¹³C{¹H, ³¹P}-DEPT-NMR and the ¹H{³¹P}-NMR spectrum of 1 reveals the presence of two symmetrical configurational isomers 1a and 1c and one asymmetrical diastereomer 1b . This would only be possible, if 1 is 3,4,10,11-tetraisopropyl-hexacyclo[6.6.0.0^2,6.0^5,14.0^7,12.0^9,13]tetradecaphosphane. When crystallizing 1 pure 1a precipitates, which at +10°C in solution is retransformed into the isomeric mixture 1a , 1b , 1c by inversion of the configuration.     

Beiträge zur Chemie des Phosphors. 233. Li3P7O3 und Li2HP7O2 – die ersten Oxido-heptaphosphane(3)

Contributions to the Chemistry of Phosphorus. 233. Li₃P₇O₃ and Li₂HP₇O₂ – the First Oxido Heptaphosphanes(3) The novel oxido heptaphosphanes(3) Li₃P₇O₃ ( 1 ) and Li₂HP₇O₂ ( 2 ) have been obtained by the reaction of trilithium heptaphosphide with cumene hydroperoxide. The compounds 1 and 2 are also formed from lithium pentaphosphacyclopentadienide and cumene hydroperoxide. They are sensitive to oxidation and are pale yellow solids whose structures have been elucidated by means of NMR and IR spectroscopic investigations. In each case, the oxygen atoms are bonded as lithiumoxido groups exocyclically to the heptaphosphanortricyclene skeleton.     

Beiträge zur Chemie des Phosphors. 138. P5(t-Bu)4H – das erste Derivat von iso-P5H5

Contributions to the Chemistry of Phosphorus. 138. P₅(t-Bu)₄H — the First Derivative of iso-P₅H₅ The thermolysis of 1,2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H, yields under suitable conditions the compound P₅(t-Bu)₄H ( 1 ) as the main product. Besides, the tert-butylphosphanes t-BuPH₂, P₆(t-Bu)₅H ( 2 ), H₂(t-BuP)₃, and (t-BuP)₄ are formed. 1 has been isolated in the pure state and structurally characterized as 1-(tert-butylphosphino)-2,3,4-tri-tert-butyl-cyclotetraphosphane. Hence, compound 1 is a derivative of iso-P₅H₅ with a branched phosphorus skeleton built up by a four-membered ring and a phosphorus side chain.     

Beiträge zur Chemie des Phosphors. 157. Dilithium-hexadecaphosphid,Li2P16: Darstellung aus Li2HP7 und 31P-NMR-spektroskopische Strukturbestimmung

Contributions to the Chemistry of Phosphorus. 157. Dilithium Hexadecaphosphide, Li₂P₁₆: Preparation from Li₂HP₇ and Structure Determination by ³¹P-NMR Spectroscopy . Dilithium hexadecaphosphide, Li₂P₁₆ ( 1 ), is purely obtained as a crystalline solvent adduct Li₂P₁₆ · 8 THF by the disproportionation of Li₂HP₇ in tetrahydrofuran under suitable conditions. The constitution of 1 has been deduced from its 1D- and 2D-³¹P-NMR spectrum (in dimethylformamide). The structure of the P₁₆^2? ion in solution is identical with that in solid (Ph₄P)₂P₁₆ [20]. As a conjuncto-phosphane the P₁₆^2? is made up of two P₉(3)^?-unit groups analogous to deltacyclane, which are linked via the diatomic bridges as a common zero-bridge.     

Beiträge zur Chemie des Phosphors. 212. Tetraisopropyl-dodecaphosphan(4), P12i-Pr4 – Darstellung,Eigenschaften und Moleküldynamik

Contributions to the Chemistry of Phosphorus. 212. Tetraisopropyldodecaphosphane(4), P₁₂i-Pr₄ – Preparation, Properties, and Molecular Dynamics According to an earlier crystal structure analysis, tetraisopropyldodecaphosphane(4) ( 1 ) exhibits the symmetry C₂, and the substituents are arranged in all-trans position [3]. We have now found by NMR spectroscopic studies that in solution a second configurational isomer of the symmetry C_S ( 1b ) exists in addition to the molecule present in the crystal ( 1a ). The transformation of 1a into 1b , which can only occur through a quasi synchronous inversion at the atoms P³ and P⁴ or P⁹ and P¹⁰, takes place at a noticeable rate already below room temperature.     

Beiträge zur Chemie des Phosphors. 219 [1]. Tetraisopropyl-octadecaphosphan(4), P18i-Pr4 – Darstellung und kernresonanzspektroskopische Strukturbestimmung

Contributions to the Chemistry of Phosphorus. 219. Tetraisopropyloctadecaphosphane(4), P₁₈i-Pr₄ — Preparation and Structure Determination by Nuclear Magnetic Resonance Tetraisopropyloctadecaphosphane(4) ( 1 ) has been obtained by reaction of i-PrPCl₂ with P₄ and magnesium and subsequent thermolysis of the crude reaction product, and has been isolated in 95% purity. According to NMR-spectroscopic investigations, 1 contains a conjuncto-phosphane skeleton consisting of a P₁₁(5)- and a P₉(3)-structural element analogous to that of deltacyclane, joined through a common P₂-bridge. Thus, 1 is 8,14,16, 18-tetraisopropyloctacyclo[13.2.1.0^2,13.0^3,11.0^4,9.0^5,7.0^6,10.0^12,17]octadecaphosphane. Compound 1 is formed as a mixture of two configurational isomers 1 a and 1 b , which differ from each other in their spatial arrangements of the isopropyl group at P₈.     

Beiträge zur Chemie des Phosphors. 179. Triisopropyl-undecaphosphan(3), P11(i-Pr)3 – Darstellung,Eigenschaften und Moleküldynamik

Contributions to the Chemistry of Phosphorus. 179. Triisopropyl-undecaphosphane(3), P₁₁(i-Pr)₃ – Preparation, Properties, and Molecular Dynamics Triisopropyl-undecaphosphane(3) ( 1 ) has been obtained by reacting i-PrPCl₂, P₄, and magnesium and subsequently thermolysing the crude reaction product, and has been isolated in pure form. According to a two dimensional ³¹{¹H} n.m.r. spectrum 1 is a 4, 7, 11-triisopropylpentacyclo[6.3.0.0^2,6.0^3,10. 0^5,9]undecaphosphane. Compound 1 is formed as a mixture of two configurational isomers 1a and 1b , which differ from each other in the orientation of the isopropyl groups. When crystallizing pure 1b precipitates, which in solution is retransformed into the isomeric mixture 1a , 1b by inversion of the configuration.     

Beiträge zur Chemie des Phosphors. 170. Konstitutions- und Konfigurationsisomere von Hexaphosphan(8), P6H8

Contributions to the Chemistry of Phosphorus. 170. Constitutional and Configurational Isomers of Hexaphosphane(8), P₆H₈ Phosphane mixtures containing 5–10 P-% of hexaphosphane(8), P₆H₈, are obtained by thermolysis of diphosphane, P₂H₄, or as residue from distillation of crude diphosphane [3]. By complete analysis of the ³¹P{¹H}-NMR spectrum on the basis of selective population transfer experiments, the following P₆H₈-isomers with a branched phosphorus skeleton have been identified and structurally characterized: the two diastereomers of 2-phosphinopentaphosphane ( 1a : erythro; 1b : threo), two of the three diastereomers of 3-phosphinopentaphosphane ( 2a : erythro, erythro; 2b : erythro, threo), and the highly symmetric 2,3-diphosphinotetraphosphane ( 3 ). The correlation between the diastereomers and the observed spin systems results from the preferred gauche orientation of neighboring free electron pairs, the dependence of ¹J(PP) on dihedral angles as well as the ³J(PP) and ⁴J(PP) long range couplings. Any indications of the diastereomers of n-P₆H₈ with an unbranched chain of phosphorus atoms have not been found.     

Beiträge zur Chemie des Phosphors. 231. Li3P7S3 und Li2HP7S2 — die ersten Sulfido-heptaphosphane(3)

Contributions to the Chemistry of Phosphorus. 231. Li₃P₇S₃ and Li₂HP₇S₂ — the First Sulfido Heptaphosphanes(3) The novel sulfido heptaphosphanes(3) Li₃P₇S₃ ( 1 ) and Li₂HP₇S₂ ( 2 ) have been obtained by the reaction of Li₃P₇ with sulfur in tetrahydrofuran under suitable conditions. The compounds 1 and 2 are also formed from LiP₅ and sulfur and are only stable in solution below room temperature. According to a complete analysis of the ³¹P{¹H}-NMR spectra, in each case, the sulfur atoms are bonded as sulfido groups exocyclically to the heptaphosphanortricyclene skeleton. Compound 2 reacts with chloro(trimethyl)silane or acetylacetone at one of the two sulfido groups while compound 1 does not form any product with retention of the P₇(3) framework.     

Beiträge zur Chemie des Phosphors. 167 [1, 2]. Konstitutions- und Konfigurationsisomere von Pentaphosphan(7), P5H7

Contributions to the Chemistry of Phosphorus. 167. Constitutional and Configurational Isomers of Pentaphosphane(7), P₅H₇ Phosphane mixtures containing 10—15 P-% of pentaphosphane(7), P₅H₇, are obtained by thermolysis of diphosphane, P₂H₄, or as residue from distillation of crude diphosphane [3]. According to the complete analysis of the ³¹P{¹H}-NMR spectrum on the basis of selective population transfer experiments, P₅H₇ exists as a mixture of three diastereomers of n-P₅H₇ — 1a (erythro, erythro), 1b (erythro, threo), 1c (threo, threo) — and of the constitutional isomer 2-phosphinotetraphosphane 2 (iso-P₅H₇, largest relative isomeric abundance). The correlation between the diastereomers and the observed spin systems results from the preferred gauche orientation of neighboring free electron pairs, the dependence of ¹J(PP) on dihedral angles, and the ³J(PP) long range couplings. From the ³¹P-NMR data of the phosphane molecules P_nH_n+2 with n = 1—5 general relationships for the δ(³¹P) values and the ¹J(PP) coupling constants of chain-type phosphorus hydrides as a function of their structural parameters are derived.     

Beiträge zur Chemie des Phosphors. 223. Hexaisopropyl-icosaphosphan(6), P20i-Pr6 — Darstellung und kernresonanz-spektroskopische Strukturbestimmung von zwei Konstitutionsisomeren

Contributions to the Chemistry of Phosphorus. 223. Hexaisopropylicosaphosphane(6), P₂₀i? Pr₆ — Preparation and Structure Determination of Two Constitutional Isomers by Nuclear Magnetic Resonance Hexaisopropyl-icosaphosphane(6) has been obtained by reaction of i-PrPCl₂ with P₄ and magnesium and subsequent thermolysis of the crude reaction product. The compound is formed as a mixture of two constitutional isomers 1 and 2 of equal abundance, which have been almost purely isolated by HPLC as a mixture of the diastereomers 1 a , 1 b and in the form of the separate configurational isomers 2 a and 2 b , respectively. According to NMR-spectroscopic investigations, the new conjuncto-phosphane skeletons of 1 and 2 consist of a P₁₃(5)- and a P₉(5)-structural element analogous to that of brexane and of two P₁₁(5)-partial skeletons, respectively, joined in each case through a common P₂-bridge. Thus, 1 is 6,7,9,16,17,20-hexaisopropyloctacyclo[10.8.0.0^2,14.0^3,11.0^4,8.0^5,10.0^13,18.0^15,19]icosaphosphane and 2 is 7,9,15,17,19,20-hexaisopropyl-octacyclo[14.2.1.1^5,8.0^2,14.0^3,12.0^4,10.0^6,11.0^13,18]icosaphosphane. The phosphorus hydrogen compound P₂₀H₆ [22, 2c] should exhibit the same constitutional isomerism.     

Beiträge zur Chemie des Hydrazins und seiner Derivate. XVIII. Darstellung und Eigenschaften von Salzen des Triazans

The reaction of N₃H₇SO₄ with barium compounds BaX₂ in aqueous solutions yields under precipitation of BaSO₄ solutions which contain the corresponding salts of triazane N₃H₆X (X = NO, ClO, Cl^?, CH₃COO^?, N₃, CN^?, Br^?, OH^?). Due to the instability of the triazanium ion, NH₂? NH₂? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm + } $\end{document}H₂, the solid triazanium salts could only be isolated in mixture with the also formed BaSO₄. The properties of these compounds are described.     

Beiträge zur Chemie des Phosphors. 172. Existenz und Charakterisierung des Pentaphosphacyclopentadienid-Anions,P5−, des Tetraphosphacyclopentadienid-Ions,P4CH−, und des Triphosphacyclobutenid-Ions,P3CH2−

Contributions to the Chemistry of Phosphorus. 172. Existence and Characterization of the Pentaphosphacyclopentadienide Anion, P₅^?, the Tetraphosphacyclopentadienide Ion, P₄CH^?, and the Triphosphacyclobutenide Ion, P₃CH₂^? The pentaphosphacyclopentadienide anion, P₅^? ( 1 ), the tetraphosphacyclopentadienide ion, P₄CH^?( 2 ), and the triphosphacyclobutenide ion, P₃CH₂^?( 3 ), are formed besides other polyphosphides by the nucleophilic cleavage of white phosphorus with sodium in diglyme. 1 also results from the reaction of lithium dihydrogenphosphide with white phosphorus and can be obtained pure in the form of a LiP₅ solution after separating the other products. The common structural feature of 1, 2 , and 3 are rings with unsubstituted P atoms of coordination number 2 that are stabilized by mesomerism.     

Beiträge zur Chemie des Phosphors. 169. 31P-NMR-spektroskopischer Nachweis und Struktur von Hexaphosphan(6), P6H6

Contributions to the Chemistry of Phosphorus. 169. ³¹P-NMR Spectroscopic Detection and Structure of Hexaphosphane(6), P₆H₆ Phosphane mixtures containing 5–10 P-% of hexaphosphane(6), P₆H₆, are obtained by thermolysis of a mixture of chain-type phosphorus hydrides P_nH_n+2 (n = 2–7) at 25–35°C. According to the complete analysis of the ³¹P{¹H}-NMR spectrum on the basis of selective population transfer experiments, P₆H₆ has the constitution of 1-phosphino-cyclopentaphosphane. An indication of the constitutional isomer with a six-membered phosphorus-ring and all trans orientation of the hydrogen atoms and the free electron pairs, respectively, has not been found. From the δ(³¹P) data of the phosphanes with five-membered rings P_nH_n (n = 5, 6) a relationship for the chemical shifts of this class of compounds as a function of their structural parameters is derived.     

Beiträge zur Chemie des Phosphors. 87. 1,2-Di-tert-butyl-3-iso-propyl-cyclotriphosphan,ein stabiles gemischt-substituiertes Cyclotriphosphan

Contributions to the Chemistry of Phosphorus. 87. 1,2-Di-tert-butyl-3-iso-propyl-cylclotriphosphane, a Stable Mixed-substituted Cyclotriphosphane The first kinetically stable mixed-substituted cyclotriphosphane, 1,2-di-tert-butyl-3-iso-propyl-cyclotriphosphane, (PBu^t)₂(PPrⁱ) ( 1 ), was synthesized by [2+1]-cyclocondensation of K(Bu^t)P–P(Bu^t)K with PrⁱPCl₂ in n-pentane. Mainly (PBu^t)₄ as well as mixed-substituted cyclotetra- and cyclopentaphosphanes are formed as by-products. 1 could be isolated in a pure state by high vacuum distillation and was thoroughly characterized. It forms two diastereomers, the more stable of which with a cis-standing tert-butyl and iso-propyl group can be stored without decomposition under inert conditions at room temperature for several days. Through thermolysis of 1 beside other alkylcyclophosphanes the mixed-substituted cyclotetraphosphanes (PBu^t)₂(PPrⁱ)₂ ( 2 ) and (PBu^t)₃(PPrⁱ) ( 3 ) are formed and their ³¹P NMR parameters are reported.     

Beiträge zur Chemie des Phosphors. 183. Lithium-tetrahydrogenheptaphosphid und Lithium-octa-hydrogenheptaphosphid

Contributions to the Chemistry of Phosphorus. 183. Lithium Tetrahydrogen Heptaphosphide and Lithium Octahydrogen Heptaphosphide Lithium tetrahydrogen heptaphosphide, LiH₄P₇ ( 1 ), and lithium octahydrogen heptaphosphide, LiH₈P₇ ( 2 ), belong to the first reaction products of the metalation of P₂H₄ with n-butyllithium that can be identified. Both compounds are also formed on reaction of Li₃P₇ with excess P₂H₄. 1 also results from the reaction of LiH₄P₅ with P₂H₄. Whereas 1 can be isolated as an orange-red crystalline solvent adduct in a purity of 60-70 per cent, 2 cannot be enriched further due to its extreme reactivity. The composition and the structure of 1 and 2 have been elucidated from their ³¹P-NMR spectra. Hence, 1 has a P₇ skeleton analogous to that of norbornane, whereas 2 as a precursor in the formation of 1 from P₂H₄ and n-BuLi is an open-chain doubly branched heptaphosphide.     

Beiträge zur Chemie der Alkylverbindugen von Übergangsmetallen. XXIX. Dibenzylmangan – Darstellung und Reaktionen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXIX. Dibenzyl Manganese – Preparation and Reactions Manganese(II) acetylacetonate reacts with tribenzyl aluminium and dibenzyl magnesium forming the yellow complexes 3(C₆H₅CH₂)₂Mn · Al(acac)₃ and (C₆H₅CH₂)₂Mn · Mg(acac)₂ Dibenzyl manganese is also formed at the reaction of dibenzyl magnesium or benzyl magnesium chloride with MnCl₂ · 1.5 THF and was separated as the dioxan complex (C₆H₅CH₂)₂Mn · 2C₄H₈O₂, the ligands of which can be removed to a great extent in vacuum. Dibenzyl manganese reacts with CO₂, CS₂ and SO₂ with insertion into the Mn–C-bonds. The corresponding manganese compounds were isolated and furtherly characterized.     

Beiträge zur Chemie des Siliciums und Germaniums. XXXIII [1]. Zur Darstellung von Kaliumsilyl

Reines, monoglyme- und kaliumhydridfreies, kristallines Kaliumsilyl wird aus Monosilan und Na/K-Legierung in Monoglyme unter Anwendung einer speziellen Art der Dosierung von Monosilan erhalten. Die analytische Charakterisierung der Verbindung ist durch Hydrolyse sowie durch Umsetzung mit Benzylchlorid und nachfolgende gaschromatographische Untersuchung des Reaktionsproduktes möglich. Löslichkeitsuntersuchungen von Kaliumsilyl in verschiedenen Solventien haben in Monoglyme eine zunehmende Löslichkeit mit abnehmender Temperatur ergeben. Die Leitfähigkeit einer Lösung von Kaliumsilyl in Monoglyme ist gemessen worden. Contributions to the Chemistry of Silicon and Germanium. XXXIII. On the Preparation of Potassium Silyl Pure, crystalline potassium silyl, free of glyme and potassium hydride, is prepared from monosilane and Na/K alloy, using a special method of dosing the monosilane. The substance was characterized by hydrolysis and by gaschromatographic investigation of the products from its reaction with benzyl chloride. Studying the solubility of potassium silyl in different solvents an increasing solubility in glyme is observed while the temperature is lowered. The conductivity of a solution of potassium silyl in glyme has been measured.