Beiträge zur Chemie des Phosphors. 221 [1]. Stannylsubstituierte Bicyclo [1.1.0]tetraphosphane: Bildung und Eigenschaften von R3Sn(H)P4 (R  CH3, C6H5, c-C6H11, o-C7H7)

Contributions to the Chemistry of Phosphorus. 221. Stannyl-Substituted Bicyclo[1.1.0]tetraphosphanes: Formation and properties of R₃Sn(H)P₄ (R ? CH₃, C₆H₅, c-C₆H₁₁, o-C₇H₇) The unsymmetrically substituted bicyclo[1.1.0]tetraphosphanes Me₃Sn(H)P₄ ( 1 ), Ph₃Sn(H)P₄ ( 2 ), (c-Hex)₃Sn(H)P₄ ( 3 ) and (o-Tol)₃Sn(H)P₄ ( 4 ) have been obtained by reaction of a solution of (Na/K) HP₄ with R₃ SnCl (R ? Me, Ph, c-Hex, o-Tol) under proper conditions. The structure of the compounds 1 – 4 , which are only stable in solution, has been elucidated by means of ³¹P-NMR-spectroscopy. Whereas 3 exists at ?60°C as the exo,endo isomer, 1, 2 and 4 are fluctuating molecules at room temperature and probably invert between the three possible configurational isomers (exo,exo-, exo,endo- and endo,endo-form).     

Beiträge zur Chemie des Phosphors. 222. Pentaisopropyl-tridecaphosphan(5), P13i-Pr5– Struktur in Lösung und im Kristall

Contributions to the Chemistry of Phosphorus. 222. Pentaisopropyltridecaphosphane(5), P₁₃iPr₅ – Structure in Solution and in the Crystal In an earlier investigation [3] pentaisopropyltridecaphosphane(5) ( 1 ) had been obtained by reacting i-PrPCl₂, P₄ and magnesium and subsequently thermolysing the crude reaction product, but had been structurally characterized only incompletely. We have now corroborated the earlier postulated constitution by NMR spectroscopic studies and an X-ray structural analysis. Thus 1 is 3,4,7,10,11-pentaisopropyl-pentacyclo[7.4.0.0^2,6.0^5,13.0^8,12]tridecaphosphane. In solution two configurational isomers 1 a and 1 b exist in the relative abundance of about 2 : 1, which have the symmetry C₁ and C_s, respectively. When crystallizing pure 1 b precipitates, which at room temperature in solution is retransformed into the isomeric mixture 1 a , 1 b by inversion of the configuration. Any indications of an additional symmetric diastereomer have not been found. Obviously, in isomer 1 b the inversion barrier of the atom P⁷ is markedly higher than for the atoms of the two-atom bridges P³? P⁴ and P¹⁰? P¹¹, respectively.     

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. 230. Hexaisopropyl-tetradecaphosphan(6), P14i-Pr6, und Hexaisopropyl-hexadecaphosphan(6), P16i-Pr6 — Bildung und 31P-NMR-spektroskopische Strukturbestimmung

Contributions to the Chemistry of Phosphorus. 230. Hexaisopropyltetradecaphosphane(6), P₁₄i-Pr₆, and Hexaisopropylhexadecaphosphane(6), P₁₆i-Pr₆ — Formation and Structural Determination by ³¹P-NMR Spectroscopy Hexaisopropyltetradecaphosphane(6) ( 1 ) and hexaiso-propylhexadecaphosphane(6) ( 2 ) are formed together with other isopropylpolycyclophosphanes by the reaction of i-PrPCl₂ with P₄ and magnesium and have been enriched to 30 mol% and 10 mol%, respectively. According to ³¹P-NMR spectroscopic investigations, the novel conjuncto-phosphane skeletons of 1 and 2 are the annelation products of a P₅ ring with a P₁₁(5) or a P₁₃(5) partial skeleton, respectively, joined by a common P₂ bridge. Thus, 1 is 4,5,6,10,12,14-hexaisopropylpentacyclo-[9.2.1.0^2,9 .0^3,7 .0^8,13]tetradecaphosphane and 2 is 5,6,7,11,14,15-hexaisopropylhexacyclo[7.7.0.0^2,13 .0^3,10 .0^4,8 .0^12,16]hexadecaphosphane. The phosphorus hydrides P₁₄H₁₆ and P₁₆H₆ have the same skeletal structures which are also intermediate stages in the formation of Hittorf's phosphorus.     

Beiträge zur Chemie des Phosphors. 226. 2,3,4,6-Tetra-tert-butyl-2,4-dioxobicyclo[3.1.0]hexaphosphan,P6BuO2

Contributions to the Chemistry of Phosphorus. 226. 2,3,4,6-Tetra-tert-butyl-2,4-dioxobicyclo[3.1.0]hexaphosphane, P₆Bu O₂ Under suitable conditions, the reaction of tetra-tert-butylhexaphosphane, P₆Bu ( 1 ), with cumene hydroperoxide gives rise to the corresponding dioxide P₆BuO₂ ( 3 ) which could be isolated as the adduct P₆BuO₂ · 0.7 C₉H₁₂O₂. According to a complete analysis of the ³¹P{¹H}-NMR spectrum compound 3 is 2,3,4,6-tetra-tert-butyl-2,4-dioxobicyclo[3.1.0]hexaphosphane, in which the oxygen atoms are bonded exocyclically to the five-membered phosphorus ring of 1 . When the oxidation reaction proceeds a fission of the bicyclic P₆ skeleton takes place.     

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. 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. 217 [1]. Hexaisopropyl-octadecaphosphan(6), P18i-Pr6—Darstellung und kernresonanzspektroskopische Strukturbestimmung

Contributions to the Chemistry of Phosphorus. 217. Hexaisopropyloctadecaphosphane(6), P₁₈i-Pr₆ – Preparation and Structure Determination by Nuclear Magnetic Resonance Hexaisopropyl-octadecaphosphane(6) ( 1 ) has been obtained by reaction of i-PrPCl₂ with P₄ and magnesium and subsequent thermolysis of the crude reaction product, and has been purely isolated as a yellow solid. According to NMR-spectroscopic investigations, 1 contains a new conjuncto-phosphate skeleton consisting of a P₁₁(5)- and a P₉(5)-structural element analogous to that of brexane, joined through a common P₂-bridge. Thus, 1 is 5,7,8,14,16,18-hexaisopropyl-heptacyclo[13.2.1.0^2,13.0^3,11.0^4,9.0^6,10.0^12,17]octadecaphosphane. Compound 1 is formed as a mixture of two configurational isomers 1a and 1b , which probably differ from each other by inversion of the configuration at the (PR)₂-bridge of the P₉(5) partial structure analogous to that of brexane.     

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 Phosphors. 225 [1, 2] Lithium-pentahydrogenoctaphosphid

Contributions to the Chemistry of Phosphorus. 225. Lithium Pentahydrogen Octaphosphide Lithium pentahydrogen octaphosphide, LiH₅P₈ ( 1 ), belongs to the first reaction products of the metallation of P₂H₄ with n-butyllithium to be detected. Compound 1 is also formed in the reactions of the tricyclic heptaphosphide Li₃P₇ or the monocyclic pentaphosphide LiH₄P₅ with P₂H₄. In all cases, LiH₄P₇, LiH₈P₇, and further not yet identified polyphosphides are formed additionally. The composition and the structure of 1 have been elucidated by ³¹P-NMR studies, above all a complete analysis of its low-temperature ³¹P{¹H}-NMR spectrum. Hence, compound 1 is 7-lithium-2,5,6-trihydrogen-3-phosphino-bicyclo[2.2.1]heptaphosphide and has a norbornane-type P₇ skeleton. At room temperature 1 decomposes to furnish more phosphorus-rich lithium polyphosphides.