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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2379-2382 
    ISSN: 0009-2940
    Keywords: Steric overcrowding ; Trisphosphane, linear, bismethylene-bridged ; Molybdenum, complexes with bis- and trisphosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis[(di-tert-butylphosphanyl)methyl]methylphosphane[1]The synthesis of [(di-tert-butylphosphanyl)methyl]dimethyl-phosphane (3) and of the title compound 5 is described. 5 reacts with sulfur to form the trisulfide 6. Both 3 and 5 behave as bidentate ligands in forming the molybdenum complexes 8 and 10, which are characterized by single crystal X-ray structure determinations. 10 reacts with sulfur to yield the sulfide 11, which decomposes in solution within 6 h.
    Additional Material: 2 Ill.
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  • 12
    ISSN: 0009-2940
    Keywords: Calix[4]arenes ; Supramolecular chemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation of Phosphorus -  and Fluorine-Containing Calix[4]arene Derivatives. Conformational Analysis, Separation of the Conformers, and X-Ray Crystal Structure Analysis of a Cone ConformerHerrn Professor Helmut Werner zum 60. Geburtstag gewidmet.The Calix[4]arene 1 reacts with hexamethyldisilazane or (diethylamino)trimethylsilane to form the bis-trimethylsilyl-ated derivative 2. Treatment of 2 with PF2C1 gives the mono-and bis-difluorophosphites 3 and 4, which react with elimination of Me3SiF or PF3 to yield the monofluorophosphite derivative 5. All four OH hydrogen atoms in 1 are replaced by lithium on reaction with nBuLi with formation of the tetrali-thiated product 6. This has been allowed to react with the Pchlorophosphorinanones 7-9. From 7 the cone conformer 10a is formed, whereas in the case of 8 and 9 a mixture of all four possible conformars 11a-d and 12a-d is obtained. The pure conformers 12a-d are isolated. By refluxing the cone conformer 12a in tetrachloroethane a conformational conversion is effected. In order to evaluate its coordinating ability, 12a was allowed to react with dichloro(cycloocta-1, 5-diene)platinum(II) to form the trans-disubstituted complex 13. In the case of 12a (acetonitrile solvate) a single-crystal X-ray structure analysis has been conducted. The molecule displays a cone conformation, whereby two of the opposing phenyl rings are approximately parallel and the other two approximately perpendicular to each other.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 13
    ISSN: 0009-2940
    Keywords: Lithiation ; P ligands ; NMR spectroscopy ; Molecular structure ; Hydrogenations ; Hydroformylations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-1,1′ -binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveals the presence of P - H - O bridging bonds in the more basic tBuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearence of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanyl phenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands.
    Additional Material: 3 Ill.
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  • 14
    ISSN: 0009-2940
    Keywords: Bisphosphane, bisdichloromethylene-bridged ; Oxidation with tetrachloro-o-benzoquinone(TOB) ; σ 6 λ5-phosphorate ; Phosphorus Heterocycles ; Structure elucidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compound 3 was formed in the reaction of Cl2PCCl2PCl2 (2) with catechol in the presence of triethylamine. The reaction of 3 with tetrachloro-o-benzoquinone (TOB), 4, led to the σ3P/σ5P-species 5, and the σ5P/σ5P-species 6a/6b. 5 was stable only in solution, and its existence and identity are postulated on the basis of its 31P-NMR spectrum. The structure of 6a/6b could not be assigned unambiguously to one isomer. The reaction of 6a/6b with water yielded the phosphorate 10. The structures of 3 and 10 were determined by single crystal X-ray methods. A wide P—C—P angle (123.2°) was observed in 3. The cation of 10 is a centrosymmetric, protonated DMF dimer with O—O 241.3 pm.
    Additional Material: 2 Ill.
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  • 15
    ISSN: 0009-2940
    Keywords: Phosphoranes, organofluoro- ; Spirophosphoranes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of Fluorophosphoranes with Trimethylsilyl (Trimethylsilyloxy)acetate: Structures, NMR-Spectroscopic Studies and X-ray Investigations of Mono- and Spirocyclic (Acyloxy)phosphoranes[1]The reaction of the tetrafluorophosphoranes RPF4 (R = Me, Ph) with trimethylsilyl (trimethylsilyloxy)acetate (1) yields the corresponding monocyclic fluoro(acyloxy)phosphoranes 2 and 3 by cleavage of the Si - O bond and elimination of (CH3)3SiF. 2 and 3 were investigated by NMR spectrometry. The spirocyclic (acyloxy)phosphoranes 4-13 are formed analogously by the reaction of 1 with the fluorophosphoranes RPF4 [R = F, Me, Et, iPr, Me3SiCH2, CH2Cl, CHCl2, H2C = CH, C6H5, 2,5-(CH3)2C6H3] in a molar ratio of 2:1. Spirophosphorane 14 is synthesized by the reaction of with PhN3 in the presence of a base. The trifluorophosphoranes R2PF3 (R = Me, Ph) react with 1 to form the monocyclic fluoro(acyloxy)phosphoranes 15 and 16, where the fluorine atom occupies an axial position at trigonal-bipyramidal (TBP) phosphorus. X-ray structure analyses of 4 and 7 reveal TBP geometry at phosphorus. The acyloxy ligand is found to form a chelate ring, whereby one axial and one equatorial site at TBP phosphorus are bridged.
    Additional Material: 2 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1765-1768 
    ISSN: 0009-2940
    Keywords: Si - O Bond cleavage ; Donor-acceptor interaction ; P=O group ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation and Structures of Some Intramolecular Donor-Acceptor Complexes with the Phosphoryl Group as DonorThe reaction of [2,2-diphenyl-1-(trimethylsiloxy)ethenyl]-dimethylphosphane oxide (1) with PF5 yields 2, involving hexacoordinated phosphorus, by cleavage of the Si-O bond and elimination of (CH3)3SiF. The same compound was formed in the reaction of 1 with RPF4 (R = dimethylamino, morpholino) by cleavage of the P-N bond and elimination of the corresponding silylated amine, R2NSiMe3. The reaction of 1 with F3B · OEt2 led to the intramolecular donor-acceptor-complex 3 with a tetracoordinated boron atom. The complex 4 with penta- (or hexa)coordinated tin was prepared by reaction of 1 with tin(IV) chloride with elimination of (CH3)3SiCl. X-ray structure analyses of 2 and 3 confirm the donor-acceptor interaction between the oxygen atom of the P=O group and the PF4 or BF2 group.
    Additional Material: 2 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1247-1249 
    ISSN: 0009-2940
    Keywords: 1,5,2,4-Diazadiphosphorinane-6-one, cis-trans isomerism of ; 1,5,2,4-Diazadiphosphorinan-6-one, 2,4-disulfides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 2,4-bis(dialkylamino)-1,5-dimethyl-1,5,2,4-diazadiphos-phorinan-6-ones 1a and 1b (R = CH3, a; C2H5, b) are thermally unstable and are transformed into the bicyclic species 2 when heated to 150°C (2 Torr). The reactions of 1a and 1b with elemental sulfur lead to the P,P′-disulfides 4a and 4b as a mixture of cis and trans isomers which are separated by column chromatography. Single-crystal X-ray structure determinations were conducted on compound 2 and on the cis and trans isomers of 4b. The bicyclic compound 2 is found to display crystallographic twofold symmetry. Its structure is closely similar to that of the diphenyl analogue. For the cis and trans isomers of 4 almost ideal S-P…P-S torsion angles are observed. The isomers adopt different ring conformations.
    Additional Material: 3 Ill.
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  • 18
    ISSN: 0009-2940
    Keywords: 2,3-Dihydro-1,3-dimethyl-1,3,2-benzodiazaphosphorin-4-(1H)-ones, 2-trimethylsiloxy-, 2-oxo-, and 2-fluoro-substituted ; Equilibrium reaction ; Aminodifluorophosphanes ; Platinum complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,3-Dihydro-1,3-dimethyl-2-oxo-1,3,2δ4-benzodiazaphosphorin-4(1H)-one 1 reacted with diethylaminotrimethylsilane to give solely the 2-trimethylsiloxy-δ3-diazaphosphorinone 2. The reaction of 2 with the 2-chloro-δ3-diazaphosphorinone 3 yielded the P - O - P-bridged compound 4 in an equilibrium reaction with elimination of trimethylchlorosilane. The synthesis of the P-difluorophosphite-substituted δ3-benzodiaza-phosphorinone 6 was effected by the reaction of chlorodifluorophosphane (5) with 1 in the presence of triethylamine in a 1:1 molar ratio, or in the reaction of 5 with 2 or 4. The reaction of 5 with 6 led, with elimination of μ-oxo-bis(difluoro-phosphane), to the P(III)Cl species 3, 5 reacted with N,N'-dimethylanthranilamide in the presence of triethylamine in a 2:1:2 molar ratio to give the N,N'-bis(difluorophosphane) derivative 9, as evidenced by low temperature (-30°C) 19F-and 31P-NMR data. At room temperature the 2-fluoro-δ3-diazaphosphorinone 10 was formed from 9 with intramolecular elimination of phosphorus trifluoride. 2-Chloroethyl- or bis(2-chloroethyl)aminodifluorophosphane 11 and 12 were obtained in the reaction of 5 with 2-chloroethyl- or bis(2-chloroethyl)amine hydrochloride in the presence of triethylamine in a 1:1:2 molar ratio. 12 reacted with (COD)PtCl2 (COD = 1,5-cyclooctadiene) in a 2:1 molar ratio to give the {cis-bis[bis(2-chloroethyl)aminodifluorophosphane]dichloro}platinum(II) complex 13. The characterization of 2, 4, 6, and 11-13 is based on their NMR and mass spectra. The structures of 10 and 13 were established by single-crystal X-ray analysis. 10 crystallizes with two independent molecules. Both six-membered heterocycles display an envelope conformation with the phosphorus atoms 36.9 and 50.4 pm, respectively, out of the plane. The phosphorus atoms have pyramidal coordination geometry. The cis-configuration at platinum(II) in the complex 13 was confirmed; two ligands (12) are coordinated to PtII via phosphorus. The platinum atom has a distorted square-planar coordination geometry.
    Additional Material: 3 Ill.
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  • 19
    ISSN: 0009-2940
    Keywords: Phospholenes ; Phosphepines ; Ring expansion reactions ; Perfluorinated diketones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Phospholene and Phosphepine Derivatives from λ3-Phosphorus Compounds and Hexafluoroacetone or Perfluorinated α-DiketonesThe reaction of the bis(2-chloroethyl)amino-substituted benzoxazaphosphorinone 1 with hexafluoroacetone (HFA) proceeds with insertion of the carbonyl group of HFA into the heterocycle of 1 to form the oxazaphosphepinedione 2. Triethyl phosphite (3) and triphenyl phosphite (4) react with the perfluorinated diketones 5 and 6 with formation of the pentaoxyphosphoranes 7-10 containing a dioxaphospholene ring system. The reaction of the (2-chloroethyl)amino- and bis(2-chloroethyl)amino-substituted 1,3,5,2-triazaphosphorinanediones 11-14 with the perfluorinated diketone C2F5C(:O)C(:O)CF3 (15) furnishes spirophosphorane derivatives with the dioxaphospholene ring system, 16 and 17, in two cases only. Compound 1 and 2-[bis(2-chloroethyl)-amino]-4H-1,3,2-benzodioxaphosphorin-4-one (18) react with the perfluorinated α-diketones 5 and 6 with insertion of the diketones into the heterocycle of 1 and 18 with formation of compounds 19-22 containing dioxa- and oxazaphosphepinone ring systems. The expected oxidative addition of the diketones to λ3P with formation of spirophosphoranes was not observed. Compounds 19-22 were obtained as mixtures of isomers (19a/b-22a/b). Single crystal X-ray structure analyses were conducted on 2 and 9. The seven-membered ring of 2 displays a “tub” conformation, with the O and benzo C atoms lying out of the plane of the other four atoms. The two independent molecules of 9 are similar, but differ in the degree of distortion from trigonal-bipyramidal geometry of phosphorus.
    Additional Material: 2 Ill.
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  • 20
    ISSN: 0009-2940
    Keywords: 1,3,5-Trimethylbiuret ; Ethylenediamine, N,N,N′-trimethyl- ; Iron complexes ; Chromium complexes ; Molybdenum complexes ; 1,3,5,2-Triazaphosphorinanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compounds with the 1,3,5,2-Triazaphosphorinane Skeleton: Synthesis and Coordination Chemistry of Novel N,N,N′-Trimethylethylenediamine-Substituted Compounds with Three-and Four-Coordinate PhosphorusSubstitution of chlorine for the N,N,N′-trimethylethylenediamine group in the 1,3,5-trimethylbiuret derivative 2 produced 4. The reaction of the 1,3,5,2-triazaphosphorinane 4 with sulfur furnished the expected P(=S) derivative 5. Reaction of 4 with methyl iodide led to the formation of the ammonium iodide 6 by methylation of the nitrogen atom of the terminal NMe2 group while the phosphorus atom of 4 remained unaffected. The structure of 6 was confirmed by a single-crystal X-ray structure analysis. In the unusual reaction of 4 with Br2 the bromodimethylammonium-bromophosphonium dibromide 7 was formed. The reaction of 4 with Fe2(CO)9 furnished the expected Fe(CO)4 complex 8 while with (C7H8)Cr(CO)4 (C7H8=norbornadiene) 9 was obtained. In 9, norbornadiene is replaced by one molecule of 4, which is coordinated by phosphorus and the nitrogen atom of the NMe2 group. In the reaction of 4 with C7H8Mo(CO)4 (C7H8=norbornadiene) the complexes 10a and 10b were formed. In 10a, the P(III) atom of 4 is coordinated to Mo; the second coordination site at Mo(CO)4 is occupied by the nitrogen atom of the terminal NMe2 group. In 10b, the nitrogen atoms of the PN(Me) and of the NMe2 grouping are coordinated to Mo, with formation of a five-membered ring.
    Additional Material: 1 Tab.
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