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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 1566-1574 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structure and Reactions of the Phosphinic Ester Me2P(:O)OC(CF3)2C(CF3)2OHThe product obtained from the reaction of the Me3SiO-functional 1,3,2λ5-dioxaphospholane 1 with water or hydrogen chloride has the structure 2b of a phosphinate; the expected isomeric hydroxyphosphorane 2a has not been observed. The structure of 2b has been determined by X-ray crystal structure analysis. Crystals of 2b are monoclinic; space group P21/c. In the crystalline state 2b forms dimers, as a result of strong hydrogen bonding between the P(:O)-group of one molecule and the OH-group of a second molecule. Reactions of 2b with chlorotrimethylsilane in the presence of triethylamine resulted in cyclisation with formation of the phosphorane 1. With thionyl chloride 2b gave the cyclic chlorophosphorane 3, while 2b and 3 reacted with formation of the cyclic anhydride 4 of the hypothetical hydroxyphosphorane 2a.
    Notes: Das Produkt der Umsetzung des Me3SiO-funktionellen 1,3,2λ5-Dioxaphospholans 1 mit Wasser oder Chlorwasserstoff besitzt die Konstitution 2b eines Phosphinsäureesters; das erwartete isomere Hydroxyphosphoran 2a wird nicht beobachtet. Die Struktur von 2b wurde durch Röntgen-analyse bestimmt. 2b kristallisiert monoklin, Raumgruppe P21/c, und bildet im kristallinen Zu-stand Dimere, in denen starke Wasserstoffbrückenbindungen zwischen der P(:O)-Gruppe eines Moleküls und der OH-Gruppe eines zweiten Moleküls vorliegen. Durch Umsetzung von 2b mit Chlortrimethylsilan in Gegenwart von Triethylamin erfolgt Cyclisierung zum Phosphoran 1. Umsetzung von 2b mit Thionylchlorid liefert das cyclische Chlorphosphoran 3, während aus 2b mit 3 das Anhydrid 4 des hypothetischen Hydroxyphosphorans 2a gebildet wird.
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  • 2
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Coordinated Ligands, VII. Syntheses and Reactions of Transition Metal Carbonyl Complexes of PH-Functional Di-, Tri-, and TetraphosphanesThe synthesis of complexes of PH-functional diphosphanes (CO)mM(PhPH—PR2)n (M=Mo, m = 4, 5, n = 2, 1, R=Ph, tBu; M=Fe, m = 4, n = 1, R=Ph) (7 - 10) and of 1,2,3-triphenyltriphosphane (CO)mM—PPhH—PPh—PPhH—M(CO)m (M=Mo, Fe, m = 5, 4) (13, 14) is reported. The availability of PH-functional groups as well as uncoordinated P-atoms in these compounds permits the formation of new P—P-bonds and of heterometallic complexes such as (CO)5Mo(PhPH—PPh2)Ni(CO)3 (16) or (CO)5Mo—PPhH—PPh[Ni(CO)3]PPhH—Mo-(CO)5 (17). The 1H- and 31P NMR spectra of the complexes 4 - 10 and 13 - 20 are discussed. For complexes of 1,1,2,3,3-pentaphenyltriphosphane, (Ph2P)2PPh—M(CO)m (M=Mo, Fe, m = 5, 4) the migration of the (CO)mM group from the medial to the terminal position of the P3-skeleton could be observed by means of 31P{1H} NMR spectroscopy.
    Notes: Die Synthese von Komplexen PH-funktioneller Diphosphane (CO)mM(PhPH—PR2)n (M=Mo, m = 4, 5, n = 2, 1, R=Ph, tBu; M=Fe, m = 4, n = 1, R=Ph) (7 - 10) und des 1,2,3-Triphenyltriphosphans (CO)mM—PPhH—PPh—PPhH—M(CO)m (M=Mo, Fe, m = 5, 4) (13, 14) wird beschrieben. Die Verfügbarkeit von PH-Funktionen sowie von nicht-koordinativ gebundenen P-Atomen in diesen Verbindungen erlaubt die Knüpfung weiterer P—P-Bindungen und die Bildung heterometallischer Komplexe, z. B. (CO)5Mo(PhPH—PPh2)Ni(CO)3 (16) oder (CO)5Mo—PPhH—PPh[Ni(CO)3]PPhH—Mo(CO)5 (17). Die 1H- und 31P-NMR-Spektren der Komplexverbindungen 4 - 10 sowie 13 - 20 werden diskutiert. Für Komplexe des 1,1,2,3,3-Pentaphenyltriphosphans, (Ph2P)2PPh—M(CO)m (M=Mo, Fe, m = 5, 4) (18, 19) konnte 31P{1H}-NMR-spektroskopisch die Wanderung der (CO)mM-Fragmente von der medialen in die terminale Position des P3-Gerüstes nachgewiesen werden.
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  • 3
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structure and Reactions of 2,2′-Oxybis[2,2-dimethyl-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2λ5-dioxaphospholane]The structure of the title compound 3 has been determined by X-ray diffraction. 3 was found to crystallize in the monoclinic system (space group P21/c). Two crystallographically independent molecules are observed in the crystal lattice which differ with regard to the P - O - P angle [147.3(3)° and 150.8(3)°, respectively]. Formation of 3 has been observed in the reaction of the chlorophosphorane Me2P(pfp)Cl (2; pfp = perfluoropinacolyl) with NaHCO3, and of the siloxyphosphorane Me2P(pfp)OSiMe3 (1) with Me2P(= O)Cl. Cleavage of 3 with methanol furnishes the previously known compound Me2P(pfp)OMe (5) and the acyclic phosphinic acid ester Me2P(= O)OC(CF3)2C(CF3)2OH (4b). Reaction of 3 with water leads to exclusive formation of 4b; the isomeric hydroxyphosphorane Me2P(pfp)OH (4a) has not been observed.
    Notes: Die Struktur der monoklin (Raumgruppe P21/c) kristallisierenden Titelverbindung 3 wurde durch Röntgenstrukturanalyse bestimmt (Abb. 1-3). Im Kristallgitter werden zwei kristallographisch unabhängige Moleküle beobachtet, die sich in der Groβe des P - O - P-Winkels unterscheiden [147.3(3)° bzw. 150.8(3)°]. 3 bildet sich bei der Umsetzung des Chlorphosphorans Me2P(pfp)Cl (2; pfp = perfluorpinakolyl) mit NaHCO3 sowie aus dem Siloxyphosphoran Me2P(pfp)OSiMe3 (1) mit Me2P(= O)Cl. Die Spaltung von 3 mit Methanol liefert die bereits bekannte Verbindung Me2P(pfp)OMe (5) und den acyclischen Phosphinsäureester Me2P(= O)OC(CF3)2C(CF3)2OH (4b). Die Umsetzung von 3 mit H2O führt ausschließlich zu 4b; die Bildung des isomeren Hydroxyphosphorans Me2P(pfp)OH (4a) wird nicht beobachtet.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1465-1471 
    ISSN: 0009-2940
    Keywords: Bis(perfluoropinacolyl)phosphoranes ; Di-λ3-phosphorus compounds, methylene-bridged ; Hexafluoroacetone ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Di- and Trimethylene-Bridged Diphosphorus(III) Compounds: Synthesis and Reaction with HexafluoroacetoneA number of methylene-bridged diphosphorus(III) compounds of type Me(X)P(CH2)nP(X)Me (X = OSiMe3, n = 2: 3a; n = 3: 3b; X = Cl, n = 3: 10; X = NMe2, n = 3: 13) were synthesized in a sequence of reactions, and their interaction with hexafluoroacetone (HFA) (1) was investigated. For the bisphosphoranes formed through twofold oxidative addition of HFA at each λ3-P atom the symmetrical 1,3,2-dioxaphospholane structure (with λ5-P) was established in the case of X = OSiMe3 (n = 2: 4a; n = 3: 4b) and NMe2 (n = 3: 15). The bisphosphorane resulting from the reaction of Me(Cl)P(CH2)3P(Cl)Me (10) with HFA was found to involve the unsymmetrical 1,4,3-dioxaphospholane ring system 11. This was found to undergo a transformation at temperatures above 110°C to a bisphosphorane 12 involving a 1,2λ5-oxaphosphetane ring structure. The course of the reaction of bisphosphoranes containing OSiMe3 substituents at phosphorus with thionyl chloride was variable: while the propylene-bridged compound 4b (n = 3) yielded the expected bis(chlorophosphorane) with excess thionyl chloride, a λ5-P—O—λ5-P anhydride 8a was formed from the ethylene-bridged precursor 4a (n = 2). The novel anhydride was of unusual stability towards nucleophiles. All new compounds were characterized by elemental analysis, mass spectrometry, and especially through their 1H-, 19F-, and 31P-NMR spectra.
    Notes: Einige Methylen-verbrückte Diphosphor(III)-Verbindungen des Typs Me(X)P(CH2)nP(X)Me (X = OSiMe3, n = 2: 3a; n = 3: 3b; X = Cl, n = 3: 10; X = NMe2, n = 3: 13) wurden in mehrstufigen Reaktionen dargestellt und ihre Umsetzung mit Hexafluoraceton (HFA) (1) untersucht. Für die durch jeweils zweifache oxidative Addition von HFA an die beiden λ3-P-Atome erhaltenen Bisphosphorane wurde für X = OSiMe3 (n = 2: 4a; n = 3: 4b) und NMe2 (n = 3: 15) die symmetrische 1,3,2-Dioxaphospholanstruktur (mit λ5-Phosphor) nachgewiesen. Für das aus Me(Cl)P(CH2)3P(Cl)Me (10) resultierende Bisphosphoran wurde hingegen die Bildung des isomeren 1,4,3-Dioxaphospholan-Ringsystems 11 beobachtet. Dieses wandelte sich oberhalb 110°C in ein Bisphosphoran mit 1,2λ5-Oxaphosphetan-Ringstruktur 12 um. Die Bisphosphorane mit Me3SiO-Substituenten am Phosphor reagierten mit Thionylchlorid unterschiedlich: während die Propylen-verbrückte Verbindung 46 (n = 3) mit überschüssigem Thionylchlorid das erwartete Bis(chlorphosphoran) 9 lieferte, bildete sich aus dem Ethylen-verbrückten Bis(trimethylsiloxyphosphoran) 4a (n = 2) das λ5-P—O—λ5-P-Anhydrid 8a, das sich gegenüber Nucleophilen als bemerkenswert stabil erwies. Die Charakterisierung der neuen Verbindungen erfolgte, außer durch Elementaranalyse und Massenspektrometrie, insbesondere durch 1H-, 19F- und 31P- NMR-Spektroskopie.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 995-999 
    ISSN: 0009-2940
    Keywords: Phosphine ; Phosphinomethylation ; Phase-transfer catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear Oligophosphaalkanes, XXV1. - Synthesis of Ph2P—CH2—PH2 and (Ph2P—CH2)2PH by Phosphinomethylation of PH3 with Phase-Transfer CatalysisAlkylation of Ph2PH with CH2Cl2 under phase-transfer conditions in the system dichloromethane/toluene/water affords Ph2P-CH2Cl in high yields. Depending on the reaction conditions employed Ph2P-CH2Cl reacts with PH3 in the two phase system under phase-transfer catalysis (nBu4NCl) to yield the tertiary-primary methylenebis(phosphane) Ph2P-CH2-Ph2 (2) or the PH functional triphosphaalkane Ph2P-CH2-PH-CH2-PPh2 (3), respectively. Metallation of 2 and 3 with RLi (R = nBu, tBu) and subsequent reaction with Me3siCl yields the silyl derivatives 2e and 3b, respectively. The analysis of the 1H- 13C- and 31P-NMR spectra is reported.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 391-395 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Method for the Formation of P—P Bonds  -  Synthesis of Cyclic Diphosphane MonosulfidesAttempts to synthesize the silyl ester of dimethylthiophosphorous acid Me2P—S—SiMe3 by treating diemthylphosphane sulfide Me2P(S)H with Me2N—SiMe3 almost quantitatively lead to the diphosphane monosulfide Me2P—P(S)Me2 (3b) besides (Me3Si)2S. If disecondary phosphane sulfide MeH(S)P—[CH2]n—P(S)MeH are employed instead of Me2P(S)H the monosulfides of the 1,2-diphospholanes or 1,2-diphosphinanes 7a and 7b, respectively, are obtained. Oxidative addition of tetrachloro-o-benzoquinone to 7a or 7b affords oxyphosphoranes with λ4P—λ5P bonds.
    Notes: Beim Versuch, Dimethylphosphansulfid Me2P(S)H durch Umsetzung mit Me2N—SiMe3 in den Silylester der Dimethylthiophosphorigen Säure Me2P—S—SiMe3 zu überführen, wurde neben (Me3Si)2S ausschließlich das Diphosphanmonosulfid Me2P—P(S)Me2 (3b) erhalten. Die Übertragung dieses Reaktionsprinzips auf die disekundären Phosphansulfide MeH(S)P—[CH2]n—P(S)-MeH (n = 3,4; 6a, b) macht die Monosulfide der 1,2-Diphospholane bzw. 1,2-Diphosphinane 7a bzw. 7b zugänglich. Oxidative Addition von Tetrachlor-o-benzochinon an 7a bzw. 7b liefert Oxyphosphorane mit λ4P—λ5P-Strukturelementen.
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  • 7
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 94 (1982), S. 393-393 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract.Das vollständige Manuskript dieser Zuschrift erscheint in: Angew. Chem. Suppl. 1982, 907-912
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  • 9
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N,N′-Dimethylurea-bridged Diphosphorus Compounds; Structure of a Spirophosphorane with λ5-Phosphorus as a Bridging AtomReaction of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea with MePCl2 yields the chloro-substituted diphosphine 1. With excess hexafluoroacetone 1 reacts with loss of one equivalent of MePCl2 and formation of the spirophosphorane 3 whose structure has been determined by X-ray diffraction. The geometry at phosphorus is approximately trigonal-bipyramidal. A spirophosphorane analogous to 3 is obtained by reaction of 1 with tetrachloro-o-benzoquinone (TOB). Dehalogenation of 1 furnishes the diphosphine 7 which reacts quantitatively with one equivalent of TOB to give the λ3-λ5P-diphosphorus compound 10. Attempted further oxidation of 10 with TOB at the λ3P atom leads to cleavage of the P-P bond with formation of 4 and a further spirophosphorane 9 which results, formally, from the oxidative addition of two equivalents of TOB to a PMe unit. Formation of 4 and 9 is also observed upon reaction of 7 with more than one equivalent of TOB. In the reaction of 1 with Me2NSiMe3 the P-P-bonded compound 11 is obtained, containing one λ3-and one λ4-phosphorus atom directly bonded.
    Notes: Durch Umsetzung von N,N′-Dimethyl-N,N′-bis(trimethylsilyl)harnstoff mit MePCl2 ist das Chlor-substituierte Diphosphin 1 zugänglich. 1 reagiert mit überschüssigem Hexafluoraceton unter Abspaltung von MePCl2 zum Spirophosphoran 3, dessen Struktur durch Röntgen-Struktur-analyse bestimmt wurde. Am Phosphor liegt annähernd trigonal-bipyramidale Geometrie vor. - Durch Umsetzung von 1 mit Tetrachlor-o-benzochinon (TOB) wird ein zu 3 analoges Phosphoran 4 erhalten. Enthalogenierung von 1 liefert das Diphosphin 7, das mit einem Äquivalent TOB quantitativ zur λ3P - λ5P-Diphosphorverbindung 10 umgesetzt werden kann. Der Versuch, 10 am λ3-Phosphor mit TOB weiter zu oxidieren, führt zur Spaltung der P-P-Bindung unter Bildung von 4 und eines weiteren Spirophosphorans 9, das formal durch oxidative Addition von zwei Äquivalenten TOB an eine PMe-Einheit entsteht. 4 und 9 werden auch bei der Umsetzung von 7 mit mehr als einem Äquivalent TOB erhalten. Reaktion von 1 mit Me2NSiMe3 liefert quantitativ die Diphosphorverbindung 11, die je ein λ3- und λ4-Phosphoratom in direkter Bindung enthält.
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  • 10
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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