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  • 1
    ISSN: 0044-2313
    Keywords: Metallodiphosphenes ; alkyl isocyanides ; 1,3-diphosphapropene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal-substituted Diphosphenes. 37. Cleavage of the P=P Bond in the Metallodiphosphene (η5-C5Me5)(CO)2Fe—P=P—Mes* (Mes* = 2,4,6-tBu3C6H2) by Alkyl Isocyanides. Structure of (μ5-C5Me5)(CO)2Fe—P(NH—CH2C6H5)—C(NH—CH2C6H5)=PMes*The reaction of the metallodiphosphene (η5-C5Me5) · (CO)2Fe—P=P—Mes* (1) with two equivalents of cyclohexylisocyanide (3 a) or benzylisocyanide, respectively, afforded (E/Z)-mixtures of the 2,4-diimino-1,3-diphosphetanes (η5-C5Me5)(CO)2Fe—=NR (3 a: R = c-C6H11; 3 b: R = CH2C6H5). Complex 1 reacted with one equivalent of benzylisocyanide in an excess of benzylamine to give the 3-metallo-1,3-diphosphapropene (η5-C5Me5)(CO)2Fe—P·(NH—CH2C6H5)—C(NH—CH2C6H5)=PMes* (4). Constitution and configuration of the compounds 3 a, b, 4 were established by elemental analysis and spectra (IR, 1H-, 13C-, 31P-NMR, MS). The molecular structure of 4 was determined by x-ray diffraction analysis.
    Notes: Die Reaktion des Metallodiphosphens (η5-C5Me5)(CO)2Fe—P=P—Mes* (1) mit zwei Äquivalenten Cyclohexylisocyanid (2 a) bzw. Benzylisocyanid (2 b) liefert (E/Z)-Gemische der 2,4-Diimino-1,3-diphosphetane (η5-C5Me5)(CO)2Fe—=NR (3 a: R = c-C6H11; 3 b: R = CH2C5H5). Komplex 1 reagiert mit einem Äquivalent Benzylisocyanid in Benzylamin als Lösungsmittel zu dem 3-Metallo-1,3-diphosphapropen (η5-C5Me5)(CO)2Fe—P · (NHCH2C6H5)—C(NHCH2C6H5)=PMes* (4). Konstitution und Konfiguration der Verbindungen 3 a, b, 4 wurden durch Elementaranalysen und Spektren (IR, 1H, 13C, 31P-NMR, MS) ermittelt. Von 4 wurde zusätzlich eine Einkristall-Röntgenstrukturanalyse durchgeführt.
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  • 2
    ISSN: 0044-2313
    Keywords: Chromium, molybdenum complexes ; metal-substituted cyclotriphane ligand ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Metal-Substituted Cyclotriphosphane [(η5-C5Me5)(CO)2Fe—P]3 as Terminal η2-Ligand in Chromium and Molybdenum Tetracarbonyl ComplexesThe transition metal-substituted cyclotriphosphane [(η5-C5Me5)(CO)2Fe - P]3 reacts with (norbornadiene)M(CO)4 (M = Cr, Mo) to give monomeric complexes of the composition η2-[(η5-C5Me5)(CO)2Fe—P]3M(CO)4. The molecular structure of 2 is elucidated by X-ray analysis. The skeleton of the molecule consists of a P3 triangle with one trans and two cis-located Fe(CO)2(C5Me5) substituents. Both cis-configurated phosphorus atoms of the triangle are coordinated to a Cr(CO)4 fragment. The bond distance between the two cis orientated phosphorus atoms [2.191(5) and 2.183(6) Å] is slightly shorter with respect to the other P—P bonds [2.206(5), 2.217(5) and 2.214(5), 2.211(5) Å, respectively]. The cyclotriphosphane unit and the triangle defined by two phosphorus atoms and the metal atom enclose a dihedral angle of 44.8° and 43.4°, respectively. The Cr(CO)4 group is severely distorted by interactions with the cis-oriented (η5-C5Me5)(CO)2Fe substituent at P(3).
    Notes: Bei der Umsetzung des übergangsmetallsubstituierten Cyclotriphosphans [(η5-C5Me5)(CO)2Fe-P]3 (1) mit (Norbornadien)M(CO)4 (M = Cr, Mo) werden monomere Komplexe der Zusammensetzung η2-[(η2-C5Me5)Fe-P]3M(CO)4 (2: M = Cr; 3: M = Mo) erhalten. Die Struktur von 2 wurde durch Röntgenbeugungsanalyse bestimmt. Das Grundgerüst des Moleküls besteht aus einem Dreieck aus Phosphoratomen mit zwei cis- und einem trans-ständigen Fe(CO)2(C5Me5)-Substituenten. Die beiden cis-konfigurierten P-Atome des Dreiringes sind an ein Cr(CO)4-Fragment koordiniert. Dabei ist ihr Abstand [2, 191 (5) und 2,183(6) Å] gegenüber den beiden anderen P-P-Bindungen [2,206(5) und 2,217(5) bzw. 2,214(5) Å] geringfügig verkürzt. Die P3-Einheit und das P2Cr-Dreieck schließen einen Diederwinkel von 44,8° bzw. 43,4° ein. Aufgrund sterischer Wechselwirkungen mit dem cis-orientierten (η5-C5Me5)(CO)2FE-Substituenten an P(3) ist das Cr(CO)4-Fragment stark verzerrt.
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  • 3
    ISSN: 0044-2313
    Keywords: γ-anti effect ; 1-phosphabicyclo 3.3.1 nonane derivatives ; pentacarbonylchromium complex ; structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: γ-Anti Effect in 1-Phosphabicyclo[3.3.1]nonane Derivatives with Substituents at Phosphorus. Synthesis and Structure of Pentacarbonyl(1-phosphabicyclo[3.3.1]nonane) ChromiumIn 1-phosphabicyclo[3.3.1]nonane derivatives of the composition C8H15P(X) the CC-conformation always dominates. Changes in the chemical shifts of the bridge-head carbon atom C(5) in the 13C-NMR spectrum are only originated by the electronic influence of the substituent X at the phosphorus centre. Based on a homogeneous interpretation of the electronic interactions and with regard to Pearsons's definition of electronegativity the electronegativities of substituents at the phosphorus atom X = Cr(CO)5, Fe(CO)4, and Ni(CO)3 are estimated. These groups are placed in antiperiplanar orientation to the carbon atom C(5).The molecular structure of (1-phosphabicyclo[3.3.1]-nonane) Cr(CO)5 3 was elucidated by X-ray diffraction analysis. The molecule features the 1-phosphabicyclononane ligand in the CC-conformation, which has a nearly undistorted Cr(CO)5 unit coordinated to the phosphorus atom (d Cr—P = 2.368(1) Å).
    Notes: Bei 1-Phosphabicyclo[3.3.1]nonan-Derivaten C8H15P(X) dominiert stets die CC-Konformation. Änderungen der chemischen Verschiebung des C(5)-Brückenkopfatoms im 13C-NMR-Spektrum werden alleine durch den elektronischen Einfluß des Substituenten X am Phosphoratom hervorgerufen. Auf der Grundlage einer einheitlichen Interpretation der elektronischen Wechselwirkungen und unter Anwendung des Elektronegativitätsbegriffs von Pearson konnte die Elektronegativität der in antiperiplanarer Position zu C(5) stehenden Phosphorsubstituenten X = Cr(CO)5, Fe(CO)4, Ni(CO)3 abgeschätzt werden.Die Molekülstruktur von (1-Phosphabicyclo[3.3.1]-nonan) Cr(CO)5 (3) wurde mittels Röntgenbeugung ermittelt. Das Molekül zeigt das Bild eines 1-Phosphabicyclo[3.3.1]nonans in der CC-Konformation, an dessen Phosphoratom eine nahezu unverzerrte Cr(CO)5 Einheit (d Cr—P = 2,368(1) Å) koordiniert ist.
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  • 4
    ISSN: 0044-2313
    Keywords: Transition metal substituted diphosphenes and phosphaalkenes ; hydration ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Substituted Diphosphenes. 32. Transition Metal Substituted Acyl Phosphanes and Phosphaalkenes. 16. Hydration of (η5-C5Me5)(CO)2Fe—P=P-Mes* (Mes* = 2,4,6-t-Bu3C6H2) and (η5-C5Me5)(CO)2Fe—P=C(SiMe3)2 with 1,1,1,3,3,3-Hexafluoropropane-2,2-diole Dihydrate. X-Ray Structure Analyses of (η5-C5Me5)(CO)2Fe—P(O)(H)(PHMes*) and (η5-C5Me5)(CO)2Fe—P(O)(H)[CH(SiMe3)2]The reaction of (η5-C5Me5)(CO)2Fe—P=C(SiMe3)2 (1) with an equimolar amount of 1,1,1,3,3,3 hexafluoropropane-2,2-diol-dihydrate (hexafluoroacetone-trihydrate) leads to the addition of water to the P=C bond under formation of the phosphinito complex (η5-C5Me5)(CO)2Fe—P(O)(H)[CH(SiMe3)2] (2). Similarly the diphosphenyl complex (η5-C5Me5)(CO)2Fe—P=P-Mes* (Mes* = 2,4,6-t-Bu3C6H2) (3) is converted into (η5-C5Me5)(CO)2Fe—P(O)(H)(PHMes*) 4. The NMR spectra of the latter show the presence of the two diastereoisomers 4a and 4b. Constitution and configuration of 2 · (CF3)2C(OH)2 and 4a · 2(CF3)2C(OH)2 in the crystal were elucidated by x-ray analysis.
    Notes: Bei der Reaktion von (η5-C5Me5)(CO)2Fe—P=C(SiMe3)2 (1) mit einer äquimolaren Menge an 1,1,1,3,3,3-Hexafluorpropan-2,2-diol-Dihydrat (Hexafluoraceton-Trihydrat) wird ein Wassermolekül an die P=C-Bindung unter Bildung des Phosphinito-Komplexes (η5-C5Me5)(CO)2FeP(O)(H)[CH(SiMe3)2] (2) angelagert. In ähnlicher Weise läßt sich der Diphosphenylkomplex (η5-C5Me5)(CO)2Fe—P=P-Mes* (Mes* = 2,4,6-t-Bu3C6H2) (3) in den Komplex (η5-C5Me5)(CO)2Fe—P(O)(H)(PHMes*) 4 überführen. Bei letzterem werden NMR-spektroskopisch die beiden Diastereoisomeren 4a und 4b unterschieden. Konstitution und Konfiguration von 2 · (CF3)2C(OH)2 und 4a · 2(CF3)2C(OH)2 wurden durch Einkristall-Röntgenstrukturanalysen ermittelt.
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  • 5
    ISSN: 0044-2313
    Keywords: Metallophosphaalkenes ; hexafluoracetone ; metallodisilyl phosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal-substituted Acylphosphanes and Phosphaalkenes. 22. Insertions of Hexafluoroacetone into the PX-Bond of Metallophosphanes (η5-C5Me5)(CO)2M—PX2 (M = Fe, Ru; X = Me3Si, Cl). Structure Determination of (η5-C5Me5)(CO)2Fe—P(SiMe3)C(CF3)2(OSiMe3)Reaction of the metallophosphanes (η5-C5Me5)(CO)2M—P(SiMe3)2 (1a: M = Fe; 1b: M = Ru) with hexafluoroacetone (HFA) afforded the complexes (η5-C5Me5)(CO)2M—P(SiMe3)C(CF3)2(OSiMe3) (2a, b). The attempted synthesis of a metallophosphaalkene from 2a by thermal elimination of hexamethyldisiloxane failed. The acid catalyzed hydrolysis of 2a afforded compound (η5-C5Me5) · (CO)2Fe—P(H)C(CF3)2(OSiMe3) (3).Hexafluoracetone and (η5-C5Me5)(CO)2Fe—PCl2 (4) under-went reaction to give the metallochlorophosphan (η5-C5Me5) · (CO)2Fe—P(Cl)—O—C(CF3)2Cl (5). Constitutions and configurations of the compounds (2-5) were established by elemental analyses and spectroscopic data (IR, 1H-, 13C, 19F-, 29Si-, 31P-NMR, MS). The molecular structure of 2a was determined by x-ray diffraction analysis.
    Notes: Die Reaktion der Metallophosphane (η5-C5Me5)(CO)2M—P(SiMe3)2 (1a: M = Fe; 1b: M = Ru) mit Hexafluoraceton (HFA) liefert die Komplexe (η5-C5Me5) · (CO)2M—P(SiMe3)C(CF3)2(OSiMe3) (2a, b) Eliminierungsversuche von Hexamethyldisiloxan unter Ausbildung eines Metallophosphaalkens scheiterten. Bei der säurekatalysierten Hydrolyse von 2a entsteht die Verbindung (η5-C5Me5)(CO)2Fe—P(H)C(CF3)2(OSiMe3) (3). Hexafluoraceton und (η5-C5Me5)(CO)2Fe—PCl2 (4) reagieren zum Metallophosphan (η5-C5Me5)(CO)2Fe—P(Cl)—O—C(CF3)2Cl (5). Konstitution und Konfiguration der Verbindungen (2-5) wurden durch Elementaranalysen und spektroskopische Daten (IR, 1H-, 13C, 19F-, 29Si-, 31P-NMR sowie MS) ermittelt. Von 2a wurde zudem eine Einkristall-Röntgenstrukturanalyse durchgeführt.
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  • 6
    ISSN: 0044-2313
    Keywords: Transition metal substituted phosphaalkenes ; isophosphaalkyne complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Substituted Acylphosphanes and Phosphaalkenes. 17. Synthesis and Structure of the μ-Isophosphaalkyne Complexes [(η5-C5H5)2(CO)2Fe2(μ-CO)(μ-C=PC6H2R3)] (R = Me, iPr, tBu).Condensation of (η5-C5H5)2(CO)2Fe2(μ-CO)(μ-CSMe)}+SO3CF3- (6) with 2,4,6-R3C6H2PH(SiMe3) (7) (a: R = Me, b: R = iPr, c: R = tBu) affords the complexes (η5-C5H5)2(CO)2Fe2(μ-CO)(η-C=PC6H2R3-2,4,6) (9 a-c) with edge-bridging isophosphaalkyne ligands as confirmed by the x-ray structure analysis of 9 a.
    Notes: Die Kondensation des μ-Carbinkomplexes {(η5-C5H5)2(CO)2Fe2(μ-CO)(μ-CSMe)}+SO3CF3- (6) mit den Phosphanen 2,4,6-R3C6H2PH(SiMe3) (7) (a: R = Me, b: R = iPr, c: R = tBu) liefert die Komplexe (η5-C5H5)2(CO)2Fe2(μ-CO)(η-C=PC6H2R3-2,4,6) 9a-c, die die neuartigen Isophosphaalkine C≡P-Aryl als Brückenliganden tragen. Von 9 a wurde eine Röntgenstrukturanalyse durchgeführt.
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  • 7
    ISSN: 0044-2313
    Keywords: 1,2-Diphosphaferrocenes ; Transition Metal Complexes ; X-Ray Structure Analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,2-Diphosphaferrocenes as Ligands in Transition Metal Complexes. X-Ray Structure Analysis of [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}]Reaction of metallo-1,2-diphosphapropene (η5-tBuC5H4)(CO)2Fe—P(SiMe3)—P=C(SiMe3)2 with (Z-cyclooctene)Cr(CO)5 afforded the pentacarbonylchromium adduct of a 1,2-diphosphaferrocene [(η5-tBuC5C5H4){η5-1-[Cr(CO)5]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (1 c). Diphosphaferrocene [(η5-tBuC5H4){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 c) was formed when (η5-tBuC5H4)(CO)2FeBr was treated with (Me3Si)2P—P=C(SiMe3)2 in toluene at 60°C. Photolysis of molybdenum- and tungsten hexacarbonyl in the presence of [(η5-1,3-tBu2C5H3){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 b) gave the pentacarbonylmetal adducts 8 (M = Mo) and 9 (M = W), respectively. A corresponding manganese derivative resulted from the photochemical reaction of 2 b and (MeC5H4)Mn(CO)3. Treatment of 2 b with Co2(CO)8 yielded trinuclear [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (11). Constitution and configuration of compounds 1 c, 2 c, 8 - 11 were determined by elemental analyses and spectra (IR, 1H-, 13C-, 31P-NMR, MS). In addition the molecular structure of 11 was established by single crystal X-ray analysis.
    Notes: Die Reaktion des Metallo-1,2-diphosphapropens (η5-tBuC5H4)(CO)2Fe—P(SiMe3)—P=C(SiMe3)2 mit (Cycloocten)Cr(CO)5 liefert das Pentacarbonylchrom-Addukt eines 1,2-Diphosphaferrocenes [(η5-tBuC5H4){η5-1-[Cr(CO)5]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (1c). Das Carbonyl-metall-freie 1,2-Diphosphaferrocen [(η5-tBuC5H4){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 c) entsteht bei der Umsetzung von (η5-tBuC5H4)(CO)2FeBr mit (Me3Si)2P—P = C(SiMe3)2 in Toluol bei 60°C. Das 1,2-Diphosphaferrocen [(η5-1,3-tBu2C5H3){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 b) reagiert mit den Hexacarbonylen von Molybdän und Wolfram bei Bestrahlung zu den Pentacarbonylmetall-Addukten 8 (M = Mo) und 9 (M = W). Ein entsprechender Mangankomplex 10 wird bei der photochemischen Reaktion von 2 b mit (MeC5H4)Mn(CO)3 gebildet. Im Gegensatz hierzu entsteht bei der Behandlung von 2 b mit Co2(CO)8 der dreikernige Komplex [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3} Fe] (11). Konstitution und Konfiguration der Verbindungen 1 c, 2 c, und 8 - 11 wurden durch Elementaranalysen und Spektren (IR, 1H-, 13C-, 31P-NMR, MS) ermittelt. Von 11 wurde zusätzlich eine Einkristall-Röntgenstrukturanalyse durchgeführt.
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