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  • Chemistry  (57)
  • Nucleophilic phosphanylation  (2)
  • Methylenebisphosphanes  (1)
  • 1
    ISSN: 1434-1948
    Keywords: (R)-(+)-2,3-Epoxy-1-propanol ; 2,3-Dihydroxyalkyl phosphanes ; 1,3,2-Dioxaborolane ; 1,3-Dioxolane ring ; Enantiopure phosphanes ; Complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of (R)-(+)-2,3-epoxy-1-propanol with Ph2PH, Ph(Me)PH, or PhPH2 in the superbasic medium KOH/DMSO affords the novel chiral phosphanes 1a-1c. While 1a is obtained enantiomerically pure, 1b and the secondary phosphane 1c are formed as mixtures of diastereoisomers (RPRC, SPRC) with homochiral β carbon atoms. Derivatization of 1a with phenylboronic acid or 2,2-dimethoxypropane yields 2a and 3a with 1,3,2-dioxaborolane and 1,3-dioxolane ring systems, respectively. The X-ray structure of 2a (space group P21) reveals the presence of four molecules of R configuration in the unit cell. Nucleophilic phosphanylation of (R)-(-)-2,3-O-isopropylideneglycerol tosylate with Ph2PH, Ph(Me)PH, or PhPH2 yields chiral 3a-3d. Compound 3b was obtained enantiomerically pure. The secondary phosphane 3c has been employed in syntheses of the hydrophilic tertiary phosphanes 3e, 3f and of the novel bidentate phosphane ligands 3g, 3h, all of which have homochiral β carbon atoms. PdII complexes PdL2Cl2 of 1a, 2a, 3a (L) are formed as mixtures of cis/trans isomers. RhI complexes of 1a, 3a, and bidentate 3h have also been synthesized.
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  • 2
    ISSN: 1434-1948
    Keywords: Nucleophilic phosphanylation ; Phosphanylphthalic acid ; Phosphanylphenylacetic acid ; Benzylaminophosphanes ; Water solubility ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral- and multiply-carboxylated phosphanes and phosphanyl derivatives of benzoic and phthalic acids (1-9) are accessible in high yields by nucleophilic phosphanylation of potassium or lithium salts of commercially available fluorobenzoic and 3-fluorophthalic acids with Ph2PH, Ph2PK, PhPLi2 Ph(K)P-(CH2)3-P(K)Ph in superbasic media (DMSO/KOH) or in THF and DME. The hitherto unknown phosphanylphenylacetic acids (10-13) and phosphanylbenzylamines RR′P-C6H4-CH2- NH2 (14-19, R, R′ = H, Me, Ph) with unsubstituted amino groups were also synthesized by this method. The diphenylphosphanyl derivatives 14-16 (R, R′ = Ph) are accessible by an alternative method involving LiAlH4 reduction of the phosphanylbenzonitriles (20-22), which were obtained in high yields by nucleophilic phosphanylation of the corresponding fluoro- or chlorobenzonitriles. The novel bidentate phosphanylbenzonitrile 23 has also been obtained using this synthetic route. All compounds were completely characterized by elemental analysis, NMR spectroscopy, and mass spectrometry.
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  • 3
    ISSN: 1434-1948
    Keywords: Pd-catalyzed P-C coupling ; Nucleophilic phosphanylation ; Mono- and bisphosphonated phosphanes ; Monoesters ; Water solubility ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The triphenylphosphane derivatives 2a and 5, bearing one and two phosphonic ester groups, are accessible in high yields by consecutive Pd-catalyzed P-C coupling reactions of p-bromoiodobenzene with Ph2PH and PhPH2, respectively, and then with diethyl phosphite. Ester hydrolysis yields the highly water-soluble sodium salts of mono- and bis-phosphonated triphenylphosphane, 3a and 6, respectively. On reaction of the p- and m-fluorophenylphosphonic diethyl esters 7a, 7b with Ph2PK and subsequent ester hydrolysis the isomeric disodium (diphenylphosphano)phenylphosphonates 3a, 3b were obtained. The X-ray structure of Ph2P(C6H4-m-PO3Na2) · 5.5 H2O · iPrOH (space group Cmc21) has been determined. In the solid state, it forms a layer structure with hydrophilic (PO32-, H2O, iPrOH) and hydrophobic (Ph2P) compartments, in which the PO32- anionic groups are not engaged in coordination of the sodium cations.
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  • 4
    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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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 2900-2913 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trimethyl- und Triphenyl-germanium-, -zinn- und -bleihalogenide reagieren unter Ausschluß von Feuchtigkeit und Luftsauerstoff in Gegenwart von Triäthylamin als Halogenwasserstoff- Acceptor mit Phosphin, Phenylphosphin und Diphenylphosphin unter Bildung neuer Organometallphosphine vom Typ (R3M)3P, (R3M)2PC6H5 und R3MP(C6H5)2. Unsymmetrisch substituierte Organometallphosphine der Art (R3M)(R3M′)PC6H5 und (R3M)2(R3M)2(R3M′)P erhält man durch Umsetzung von Lithium-triorganometall-phenylphosphid bzw. Lithium- bis(triorganometall)-phosphid mit entsprechenden Organometallhalogeniden. Die Infrarot-, Raman-, 1H-NMR- und 31P-NMR-spektroskopischen Daten der Verbindungen werden mitgeteilt und diskutiert.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1383-1390 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organometalphosphine-substituted Transition Metal Complexes, VII. Organometalphosphinetricarbonylnickel(0) ComplexesThe reaction of tetracarbonyl nickel with tri(tert-butyl)phosphine, tris(trimethylsilyl)-, tris(trimethylgermyl)-, tris(trimethylstannyl)-, and tris(trimethylplumbyl)phosphine as well as with trimethylstannyldiphenylphosphine, bis(trimethylstannyl)phenylphosphine, and bis(diphenylphosphino)phenylarsine results in the elimination of one CO-ligand and the formation of corresponding organometalphosphinetricarbonylnickel(0) complexes. The i.r., 1H n.m.r., and 31P n.m.r. spectra are reported and discussed.
    Notes: Tetracarbonylnickel reagiert mit Tri(tert.-butyl)-phosphin, Tris(trimethylsilyl)-, Tris(trimethylgermyl)-, Tris(trimethylstannyl)- und Tris(trimethylplumbyl)-phosphin sowie mit Trimethylstannyl-diphenyl-phosphin, Bis(trimethylstannyl)-phenyl-phosphin und Bis(diphenylphosphino)-phenyl-arsin unter Abspaltung eines CO-Liganden und Bildung entsprechender Organometallphosphin-tricarbonyl-nickel(0)-Komplexe. Die Infrarot-, 1H-NMR-und 31P-NMR-Spektren werden mitgeteilt und diskutiert.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 106 (1973), S. 48-55 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pentacarbonyl(organometal sulfide)chromium, -molybdenum, and -tungsten ComplexesThe reaction of hexacarbonylchromium, hexacarbonylmolybdenum, or hexacarbonyltungsten with di-tert-butyl sulfide, bis(trimethylgermyl) sulfide, bis(trimethylstannyl) sulfide, or bis(trimethylplumbyl) sulfide results in the elimination of one CO ligand under formation of the corresponding pentacarbonyl(organometal sulfide)chromium(O), -molybdenum(O), or -tungsten(O) complexes Their, Raman, and 1H n m. r. spectra are discussed
    Notes: Hexacarbonylchrom, -molybdän und -wolfram reagieren mit Di-tert-butylsulfid, Bis(trimethylgermyl)sulfid, Bis(trimethylstannyl)sulfid und Bis(trimethylplumbyl)sulfid unter Abspaltung cines CO-Liganden und Bildung entsprechender Pentacarbonyl(organometallsulfid)chrom(O)-, -molybdän(O)- bzw -wolfram(O)-Komplexe. Die Infrarot-, Raman- und 1H-NMR-Spektren werden diskutiert.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 108 (1975), S. 1246-1258 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: σ-Donor-and π-Acceptor Properties of the Phosphine Ligands in Complexes of the Type of the cis-Mo(CO)4(R3—nPXn)2The first vertical ionisation potentials obtained from the u. v. photoelectron spectra are proposed to give a relative measure for the σ-donor ability of a series of phosphine ligands L (R3—nPXn, R=Me, tBu; X=H, F, Cl; n = 0-3, and (Me2N)3—nPXn, X=F, Cl, n = 0, 1, 2). Using this scale the ligands L could be classified according to their π-bonding ability by comparison of the CO-stretching frequencies and force constants within the series of complexes cis-Mo(CO)4L2. Ten complexes cis—Mo(CO)4(R3—nPXn)2 (R=Me, tBu; X=H, F, Cl; n = 1, 2) have been prepared and characterized for the first time.
    Notes: Die aus den UV-Photoelektronenspektren zu entnehmenden Ionisierungspotentiale der «freien Elektronenpaare» am Phosphor werden als ein relatives Maß für die σ-Donatorfähigkeit der Phosphinliganden L (R3—nPXn, R=Me, tBu; X=H, Cl, F; n = 0-3, und (Me2N)3—nPXn, X=F, Cl, n = 0, 1, 2) vorgeschlagen. Unter Verwendung der sich damit ergebenden Reihenfolge konnten durch Vergleich von CO-Valenzschwingungsfrequenzen und -kraftkonstanten innerhalb der Komplexreihe cis—Mo(CO)4L2 die Liganden hinsichtlich ihrer π-Acceptoreigenschaften klassifiziert werden. Zehn Komplexe cis-Mo(CO)4(R3—nPXn)2 (R=Me, tBu; X=H, F, Cl; n = 1, 2) wurden erstmals synthetisiert und charakterisiert.
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  • 9
    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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  • 10
    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, VIII. Synthesis, Reactivity, and Structure of Molybdenum- and Nickel Carbonyl Complexes of 1,3-Bis(phenylphosphino)propane1,3-Bis(phenylphosphino)propane reacts with Ni(CO)4, C7H8Mo(CO)4, and Mo(CO)6 to produce complexes of the type (CO)nM(PhPH—C3H6—PPhH) (n = 4, M=Mo; n = 2, M=Ni) and oligomers thereof. These compounds were also obtained by the reaction of phosphido complexes (CO)nM(PhPHM′)2 (n = 4, M=Mo, M′=Li; n = 2, M=Ni, M′=Li, Na) with 1,3-dibromopropane. The complexes (CO)nM(PhPH—C3H6—PPhH) may be deprotonated with methyllithium. The reactions of the phosphido complexes thus obtained are discussed. From the meso-form of (CO)2Ni(PhPH—C3H6—PPhH), which crystallizes in the space group Cmc21, an x-ray structure analysis has been performed.
    Notes: 1,3-Bis(phenylphosphino)propan reagiert mit Ni(CO)4, C7H8Mo(CO)4 und Mo(CO)6 unter Bildung von Komplexen des Typs (CO)nM(PhPH—C3H6—PPhH) (n = 4, M=Mo; n = 2, M = Ni) und deren Oligomeren. Diese Verbindungen werden auch bei Umsetzung von Phosphidokomplexen (CO)nM(PhPHM′)2 (n = 4, M=Mo, M′=Li; n = 2, M=Ni, M′=Li, Na) mit 1,3-Dibrompropan erhalten. Die Komplexe (CO)nM(PhPH—C3H6—PPhH) lassen sich mit Methyllithium deprotonieren. Über Reaktionen der dabei gebildeten Phosphidokomplexe wird berichtet.  -  Von der Mesoform von (CO)2Ni(PhPH—C3H6—PPhH) (1), das in der Raumgruppe Cmc21 kristallisiert, wurde eine Röntgenstrukturanalyse durchgeführt.
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