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  • Inorganic Chemistry  (1,777)
  • SPACE SCIENCES
  • 1995-1999  (1,777)
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  • 1
    ISSN: 0044-2313
    Keywords: Technetium Compounds ; Rhenium complexes ; X-ray diffraction ; radiopharmaceuticals ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Characterization of μ-oxo Dimeric Technetium and Rhenium Complexes with Functionalized Amine Phenolate Ligands. X-Ray Crystal Structures of [O=TcL1—O—L1Tc=O] · H2O and [O=ReL1—O—L1Re=O] Complexes (H2L1 = N,N′-bis(2-hydroxybenzyl)-1,3-diamino-2-(4-nitrobenzyl)propane)Neutral rhenium(V) and technetium(V) chelates with the tetradentate amine phenolate ligand N,N′-bis(2-hydroxybenzyl)-1,3-diamino-2(-4-nitrobenzyl)propane (H2L1) have been prepared from [MOCl4]- complexes and structurally characterized. The ligand coordinates tetradentately with deprotonation of the phenolic oxygen atoms.[O=TcL1—O—L1Tc=O] · H2O crystallizes monoclinic in the space group P21/c with a = 10.633(2), b = 13.705(1), c = 16.364(3) Å; β = 94.65(1)°, Z = 2. Two TcOL1 units with each one terminal oxo core are connected by a μ-oxo ligand. The technetium atoms are situated in distorted octahedral coordination spheres. Two distinct Tc—O bond lengths have been found for the almost linear O=Tc—O—Tc=O unit (Tc=O(terminal): 1.655(7) Å and Tc—O(μ-oxo): 1.903(1)) Å.The analogous rhenium compound crystallizes in the same space group with a = 13.302(7), b = 9.956(1), c = 17.535(9) Å; β = 106.72(2)°, Z = 2. The dimeric [O=ReL1—O—L1Re=O] complex has a structure which is very similar to that of the corresponding technetium compound.
    Notes: Ausgehend von [MOCl4]--Komplexen werden mit dem vierzähnigen Amin-Phenolato-Liganden N,N-Bis(2-hydroxybenzyl)-1,3-diamino-2-4-nitrobenzyl)propan (H2L1) Rhenium(V)- und Technetium(V)-Chelate hergestellt und strukturell charakterisiert. Es entstehen sauerstoffverbrückte, neutrale Zweikernkomplexe mit einer zentralen [O=M—O—M=O]4+-Einheit. Der Ligand koordiniert jeweils vierzähnig unter Deprotonierung der Phenolfunktionen.[O=TcL1—O—L1Tc=O] · H2O kristallisiert monoklin in der Raumgruppe P21/c mit a = 10,633(2); b = 13,705(1); c = 16,364(3) Å; β = 94,65(1)°; Z = 2. Zwei TcOL1-Einheiten mit je einem terminalen Oxo-Liganden sind über eine Sauerstoff-Brücke miteinander verknüpft. Das Metall befindet sich in einer verzerrt oktaedrischen Umgebung. Für die Tc—O-Bindung der nahezu linearen O=Tc—O—Tc=O-Einheit wurden zwei unterschiedliche Bindungsabstände bestimmt (Tc=O(terminal): 1,655(7) Å und Tc—O(Brücke): 1,903(1) Å.Die analoge Rheniumverbindung kristallisiert in der gleichen Raumgruppe mit a = 13,302(7); b = 9,956(1); c = 17,535(9) Å; β = 106,72(2)°; Z = 2. Für das ebenfalls dimere Komplexmolekül [O=ReL1—O—L1Re=O] konnten ähnliche Bindungsverhältnisse wie für sein Technetium-Analogon bestimmt werden.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1261-1265 
    ISSN: 0009-2940
    Keywords: (Cyclooctatetraene)titanium complexes ; Diphosphacyclobutadiene ; Cyclodimerization ; Phosphaalkyne ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the (η8-cyclooctatetraene)(η4-1,3- and -1,2-diphosphacyclobutadiene)titanium complexes 3a-c and 4a, b by cyclodimerization of the phosphaalkynes 2a-c [a: R = tBu, b: R = adamantyl (ad), and c: R = (iPr)(Me3Si)N] in the coordination sphere of the (η8-cyclooctatetraene)titanium complex 1 is described. The molecular structures of 3a-c and 4a, b were determined by spectroscopic methods (31P, 1H, and 13C NMR). In the case of 3a and 4a, X-ray analyses were carried out. The increased reactivity of 4a compared to 3a was utilized to separate 3a from 4a. Displacement of the 1,2-diphosphete (isolated as its cyclodimer 5) from 3b was achieved by reaction with hexachlorethane.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 981-988 
    ISSN: 0009-2940
    Keywords: Ruthenium ; Tyrosine ; Tryptophan ; Sandwich complexes ; Bioorganometallic chemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(arene)ruthenium(II) complexes of the type [(η6-cymene)Ru(η6-aa)](CF3SO3)n (2-9) containing L-tyrosine and L-tryptophan derivatives may be prepared by treatment of [(η6-cymene)Ru({CH3)2CO}3](CF3SO3)2 with the appropriate bioligand in CH2Cl2, for fully protected compounds and CF3COOH for α-amino acids (aa) with unprotected amine or carboxylic acid groups. Whereas the tyrosine and tryptophan methyl ester complexes [(η6-cymene)Ru(η6-H2tyrOMe)](CF3SO3)3 (4) and [(η6-cymene)Ru(η6-H2trpOMe)](CF3-SO3)3 (8) contain trications with protonated amino functions, the remaining compounds all exhibit dications. The crystal structure analysis of [(η6-cymene)Ru(η6-HtyrOH)](CF3SO3)2 (5) confirms a marked distortion towards an η5-oxohexadienyl coordination with deprotonation of the aromatic side chain. Although facial isomers are formed in an effectively 1:1 ratio for all tryptophan derivatives fractional crystallization allowed an X-ray structural characterization of the β-isomer of [(η6-cymene)Ru(η6-ActrpOMe)](CF3SO3)2 (6). Chemospecific labeling of the tryptophan side chain was established for the mixed dipeptide phenylalanyltryptophan.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 541-545 
    ISSN: 0044-2313
    Keywords: Dimagnesium trimolybdate(IV) ; molybdenum oxide ; preparation ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: η-Mo4O11 and Mg2Mo3O8: a New Way of Synthesis and Refinement of their Crystal StructuresMg2Mo3O8 was obtained by solid state reaction of MgI2 and MoO3 (1:1) at 200°C and subsequent crystallization at 800°C. Under the same conditions, ZnI2 and MoO3 only yielded rather impure Zn2Mo3O8; however, when ZnI2 or CdI2 and MoO3 were taken in a molar ratio of 1:2, well crystallized η-Mo4O11 was obtained. The known crystal structures of Mg2Mo3O8 and η-Mo4O11 were refined with new X-ray diffraction data (R = 0.030 and 0.059, respectively). The kind of twinning of monoclinic η-Mo4O11 is discussed.
    Notes: Durch Festkörperreaktion von MgI2 und MoO3 (1:1) bei 200°C und anschließender Kristallisation bei 800°C entsteht Mg2Mo3O8. Mit ZnI2 entsteht unter den gleichen Bedingungen nur stark verunreinigtes Zn2Mo3O8; beim Einsetzen von ZnI2 oder CdI2 und MoO3 im Molverhältnis von 1:2 wird dagegen gut kristallisiertes η-Mo4O11 erhalten. Die bekannten Kristallstrukturen von Mg3Mo8O8 und η-Mo4O11 wurden mit neuen Meßdaten verfeinert (R = 3,0 bzw. 5,9%). Die Art der Zwillingsbildung des monoklinen η-Mo4O11 wird diskutiert.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 767-773 
    ISSN: 0009-2940
    Keywords: Ether phosphanes ; Hydroxyalkylphosphanes ; Rhodium ; Asymmetric hydrogenation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically pure 1,4-bis(diphenylphosphanyl)-2-hydroxy-butane (2) and its methyl ether 1 can be conveniently prepared by starting from chiral pool substances such as malic or L-ascorbic acid. Different pathways to these compounds were elucidated. In one case an interesting migration of an acetalic OH-protective group was observed. The reaction of the bisphosphanes with Rh1 or PdII gave uniform metal complexes. On the basis of X-ray structural analysis, NMR and IR data it was concluded that in the investigated precatalysts of the type [Rh(COD)(bisphosphane)]BF4 a coordination of the alkoxy or hydroxy oxygen to the metal does not take place. Nevertheless, significant differences in enantioselectivity and activity could be observed when several prochiral substrates were hydrogenated.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1605-1609 
    ISSN: 0044-2313
    Keywords: Carbonyl coordination compounds ; α-Functionalized 2-methyl phenylphosphines ; W(CO)5 shift ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: α-Functionalized 2-Methyl Phenylphosphines, 2-(HE—CH2)—C6H4—PH2 (E = O, NR, PH) II. Coordination Behaviour with Metal Carbonyles of Cr, Mo, WThe preparation of different carbonyl substituted coordination compounds (M: Cr, Mo, W) of the phosphines 2-(HE—CH2)C6H4—PH2 (E = O, NPh, PH) is described. In one case, after deprotonation of a PH2 group a phosphine/phosphide migration of a W(CO)5 fragment is detected.
    Notes: Von drei α-funktionellen Methylphenylphosphanen 2-(HE—CH2)C6H4—PH2 (E = O, NPh, PH) werden Carbonylkomplexe der Metalle Cr, Mo, W beschrieben. In einem Fall wird nach Metallierung die Wanderung eines phosphano-koordinierten W(CO)5-Fragmentes an ein bereits W(CO)5-koordiniertes Phosphid beobachtet.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1731-1734 
    ISSN: 0044-2313
    Keywords: Indium ; Phosphorus ; Heterocubane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [{Cp(CO)3Mo}4In4(PSiMe3)4], an Organometallic In4P4-Heterocubane[{Cp(CO)3Mo}InCl2] reacts with P(SiMe3)3 in THF as solvent to form [{Cp(CO)3Mo}4In4(PSiMe3)4] 1. 1 crystallizes in the space group P1. The lattice constants (at 208 K) are: a = 1 770.1(6), b = 1 490.3(6), c = 1 317.5(6) pm, α = 76.59(4),β = 88.54(3), γ = 88.98(3)°. According to the crystal structure analysis, 1 contains a slightly distorted In4P4-core with an alternating arrangement of In and P atoms. The In atoms are coordinated roughly tetrahedrally by three PSiMe3 groups (In-P: 256.9(3)-262.3(3) pm) and a {Cp(CO)3Mo} substituent (In—Mo: 278.0(2)-279.5(3) pm).
    Notes: [{Cp(CO)3Mo}InCl2] reagiert mit P(SiMe3)3 in THF als Lösungsmittel zu [{Cp(CO)3Mo}4In4(PSiMe3)4] 1. 1 kristallisiert in der Raumgruppe P1 mit den Gitterkonstanten (bei 208 K): a = 1 770,1(6), b = 1 490,3(6), c = 1 317,5(6) pm, α = 76,59(4), β = 88,54(3), γ = 88,98(3)°. Nach dem Ergebnis der Röntgenstrukturanalyse enthält 1 ein leicht verzerrtes In4P4-Heterokubangerüst mit einer alternierenden Anordnung von In- und P-Atomen. Die Indiumatome sind etwa tetraedrisch von drei PSiMe3-Gruppen (In-P: 256,9(3)-262,3(3) pm) und einem exocyclischen {Cp(CO)3Mo}-Rest (In-Mo: 278,0(2)-279,5(3) pm) umgeben.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 889-893 
    ISSN: 0044-2313
    Keywords: Ga—P-Heterocubane ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: {(MesGa)3[GaP(H)Mes](PMes)4}, a Phosphorus-substituted Ga—P-HeterocubaneA mixture of MesGaCl2/GaCl3 (ratio 3:1) reacts with 5 equivalents of MesPLi2 in THF at -78°C to the title compound {(MesGa)3[GaP(H)Mes](PMes)4} (1) by use of the “dilution principle”. 1 can be obtained in 30% yield. Recrystallization of 1 from DME and toluene, respectively, gives 1 · 0.5 DME and 1 · toluene. 1 was characterized by NMR-, IR-, and MS-techniques. According to the X-ray structure determination of 1 · toluene, 1 has a heterocubane structure, one corner of which is substituted with an P(H)Mes group.
    Notes: Eine Mischung von MesGaCl2/GaCl3 (molares Verhältnis 3:1) reagiert mit fünf Äquivalenten MesPLi2 in THF bei -78°C zur Titelverbindung {(MesGa)3[GaP(H)Mes] · (PMes)4} (1) unter Anwendung des „Verdünnungsprinzipes“. 1 kann in 30% Ausbeute isoliert werden. Wird 1 aus DME oder Toluol umkristallisiert, werden 1 · 0,5 DME bzw. 1 · Toluol in Form von farblosen Kristallen erhalten. 1 wurde durch NMR-, IR- und MS-Untersuchungen charakterisiert. Nach den Ergebnissen der Röntgenstrukturanalysen von 1 · Toluol hat 1 eine Heterocuban-Struktur, wobei eine Ecke mit einer P(H)Mes-Gruppe substituiert ist.
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  • 9
    ISSN: 0009-2940
    Keywords: Tripod ligands ; Dinuclear cobalt complexes ; Dihydroxynaphthoquinones ; Dihydroxyanthraquinones ; Magnetism ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dinuclear Tripod Cobalt Complexes with Bridging 1,4,5,8-Tetraoxonaphthalene and 1,4,9,10-Tetraoxoanthracene Ligands: Structures, Spectroscopic, Magnetic, and Electrochemical PropertiesThe syntheses, structures, optical, magnetic, and redox properties of dinuclear tripodcobalt(II) complexes [tripod = CH3C(CH2PPh2)3] with briding 1,4,5,8-tetraoxonaphthalene 12- and 1,4,9,10-tetraoxoanthracene 22- are described. UV/Vis/NIR spectroscopy indicates interaction between the ligand and the metal orbitals. The magnetic interactions involving the two cobalt(II) centers and the bridging ligand are characterized by EPR spectroscopy and magnetic measurements and are analyzed in terms of qualitative Molecular Orbital calculations. The redox chemistry of these complexes is investigated by cyclic voltammetry and interpreted as metal-based oxidations and ligand-based reductions.
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  • 10
    ISSN: 0044-2313
    Keywords: Rhodium complexes ; Si-bridged cyclopentadienyl ligands ; bridging η3:η3 benzene ligands ; synthesis ; X-ray crystallography ; selective solvent inclusion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me2Si{3-But-C5H3Rh(C2H4)2}2]By reaction of [{(C2H4)2RhCl}2] with Na2[Me2Si(C5H4)2] or with Li2[Me2Si(3-But-C5H3)2] in THF the dinuclear silylene bridged complexes [Me2Si{C5H4Rh(C2H4)2}2] 1 and [Me2Si{3-But-C5H3Rh(C2H4)2}2] 2, respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si—C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η3:η3 benzene complex [Me2Si(C5H4Rh2)2C6H6] which cannot be separated from unreacted 1. However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3.
    Notes: Durch Umsetzung von [{(C2H4)2RhCl}2] mit Na2[Me2Si(C5H4)2] oder mit Li2[Me2Si(3-But-C5H3)2] in THF wurden die zweikernigen silylenverbrückten Komplexe [Me2Si{C5H4Rh(C2H4)2}2] 1 bzw. [Me2Si{3-But-C5H3Rh(C2H4)2}2] 2 synthetisiert. Bedingt durch die asymmetrische Substitution der Fünfringe und ihre gehinderte Rotation um die Si—C-Achsen entsteht 2 in Gestalt dreier Isomerer. Die Röntgenstrukturanalyse von aus Hexan erhaltenem 2 beweist den selektiven Einschluß von im Solvens zu ca. 17% enthaltenem Methylcyclopentan in das Kristallgitter. UV-Bestrahlung von 1 in Hexan in Gegenwart von Benzol liefert unter Abspaltung der Ethenliganden den μ-η3:η3-Benzol-Komplex [Me2Si(C5H4Rh)2C6H6] 3, der von un-umgesetztem Edukt 1 nicht abgetrennt werden kann. Dagegen gelingt die Trennung im Falle der zu 3 analogen Hexamethyl-benzol-Verbindung 4.
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