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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 931-942 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes with Biologically Important Ligands, XXXIV. Allyl-Palladium(II) and Triphenylphosphane Gold(I) Complexes with Nucleobases and NucleosidesThe reactions of (η3-allyl)Pd(μ-Cl)2Pd(η3-allyl) (A) and (COD)Rh(μ-Cl)2Rh(COD) with nucleobases and nucleosides give the complexes (η3-C3H5)Pd(L)Cl (1) (L = inosine, adenosine, guanosine, cytosine, cytidine, 2-thiouracil, 2-thiocytosine) and (COD)Rh(cytosine)Cl (2), respectively. With adenosine and purine also ligand bridged complexes (η3-C3H5)(Cl)Pd—L—Pd(Cl)(η3-C3H5) (3) have been obtained. Ph3PAuCl reacts with the anions L′ of purine, adenine, uridine, and inosine to give the complexes Ph3PAuL′ (5). Ph3PAu+ is added to both N atoms of the dianion of uracil with formation of 6. The coordination of the nucleobases is discussed on the basis of the 1H and 13C NMR spectra. The X-ray structure of Ph3PAu(adeninate) (5b) has been determined.
    Notes: Die Umsetzung von (η3-Allyl)Pd(μ-Cl)2Pd(η3-Allyl) (A) sowie von (COD)Rh(μ-Cl)2Rh(COD) mit Nucleobasen und Nucleosiden liefert unter Spaltung der Chlorobrücken die Komplexe (η3C3H5)-Pd(L)Cl (1) (L = Inosin, Adenosin, Guanosin, Cytosin, Cytidin, 2-Thiouracil, 2-Thiocytosin) bzw. (COD)Rh(Cytosin)Cl (2). Mit Adenosin und Purin wurden auch Ligand-verbrückte Komplexe (η3-C3H5)(Cl)Pd—L—Pd(Cl)(η3-C3H5) (3) erhalten. Ph3PAuCl setzt sich mit den Anionen L′ von Purin, Adenin, Uridin und Inosin zu Ph3PAuL′ (5) um; Ph3PAu+ addiert sich an die beiden N-Atome des Dianions von Uracil unter Bildung von 6. Die Koordination der Nucleobasen wird anhand der 1H- und 13C-NMR-Spektren diskutiert. Die Struktur von Ph3PAu (Adeninat) (5b) wurde röntgenographisch bestimmt.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 889-893 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The nucleophilic substitution of chloride in dichlorocyclobutenedione by carbonylmetallates gives the μ-(3,4-dioxo-1-cyclobutene-1,2-diyl) complexes LnM(C4O2)MLn 1 [MLn=Re(CO)5, Mn(CO)5, W(CO)3(η5-C5H5)] and the μ-(2-chloro-3,4-dioxo-1-cyclobuten-1-yl) complexes LnM— [MLn = Mn(Co)5, W(CO)3(η5-C5H5), Mo(CO)3(η5-C5H5)], respectively. The structure of the dirhenium complex (OC)5Re(C4O2)Re(CO)5 (1a) was determined by X-ray diffraction. The Re-C bonds are slightly shortened with respect to single bonds, Re-C=2.18(1)/2.17(1)Å [monoclinic, P21, a=7.031(1), b=11.532(1), c=11.418(1)Å, β=105.54(1)°, V=891.95Å3, dcalc=2.727 g/cm3 for Z=2, Rw=0.031 for 252 refined parameters and 3539 observables with I ≥ 2.0σ(I)].
    Notes: Die nucleophile Substitution von Chlorid in Dichlorcyclobutendion durch Carbonylmetallate liefert die μ-(3,4-Dioxo-1-cyclobuten-1,2-diyl)-Komplexe LnM(C4O2)MLn 1 [MLn=Re(CO)5, Mn(CO)5, W(CO)3(η5-C5H5)] bzw. die μ-(2-Chlor-3,4-dioxo-1-cyclobuten-1-yl)-Komplexe LnM— [MLn = Mn(Co)5, W(CO)3(η5-C5H5), Mo(CO)3(η5-C5H5)]. Nach der Röntgenstrukturanalyse des Dirhenium-Komplexes (OC)5Re-(C4O2)Re(CO)5 (1a) sind die Re-C-Bindungen gegenüber Einfachbindungen leicht verkürzt, Re-C=2.18(1)/2.17(1)Å [monoklin, P21, a=7.031(1), b=11.532(1), c=11.418(1)Å, β=105.54(1)°, V=891.95Å3, dber=2.727 g/cm3, Z=2, Rw=0.031 für 252 verfeinerte Parameter und 3539 Observablen mit I ≥ 2.0σ(I)].
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 895-900 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (OC)5ReFBF3 reacts with ethyl thiocyanate, malononitrile, cyanamide, and dicyandiamide (L) to give the ionic complexes [(OC)5ReL]+BF-4 (1). Two or three Re(CO)-3 cations, respectively, can be added to tetracyanoethene and tetracyano-p-quinodimethane (TCNQ) to give 2, 3. With the anions of tricyanoethenolate, TCNQ-, tricyanomethanide and dicyanamide (L-) the neutral compounds (OC)5ReL (4-7) are formed. The IR spectra and the X-ray structure analyses of [(OC)5Re(NCNC(NH2)2]+BF -4 (1d), (OC)5ReNCC(CN)2 (6), and of (OC)5ReNCNCN (7) show that the ligands are coordinated in all cases via the nitrile N-atom to the metal.
    Notes: (OC)5ReFBF3 setzt mit Ethylthiocyanat, Malononitril, Cyanamid und Dicyandiamid (L) zu den ionogenen Verbindungen [(OC)5ReL]+BF-4 (1) um. An Tetracyanethen sowie an Tetracyan-p-chinodimethan lassen sich zwei bzw. drei Re(CO)-3-Kationen unter Bildung von 2 und 3 addieren. Mit den Anionen Tricyanethenolat, TCNQ-, Tricyanmethanid und Dicyanamid (L-) entstehen die Neutral-Komplexe (OC)5ReL (4-7). Die IR-Spektren sowie die Röntgenstrukturanalysen von [(OC)5Re(NCNC(NH2)2]+BF -4 (1d), (OC)5ReNCC(CN)2 (6) und (OC)5ReNCNCN (7) zeigen, daß die Liganden in allen Fällen über das Nitril-N-Atom an das Metall koordiniert sind.
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  • 4
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes with Biologically Important Ligands, XLIV. - Platinum(II) and Palladium(II) as Amino Protecting Groups. Metal Complexes with Silyl Esters and Acid Chlorides as Ligands and Peptide Synthesis at the ComplexThe cleavage of the chelate ring of platinum(II) and palladium(II) glycinate, cis-, trans-M(NH2CH2COO)2 (M = Pt, Pd), by trialkylchlorosilanes results in the formation of the complexes cis-, trans-MCl2(NH2CH2CO2SiR3)2 (1). Treatment of 1 or of cis-, trans-MCl2(NH2CHRCO2H)2, respectively, with oxalyl chloride and DMF gives the α-amino acid chloride complexes cis-, trans-MCl2(NH2CHRCOCl)2 (2) from which - using N-(trimethylsilyl)-α-amino acid esters - a series of dipeptide complexes cis-, trans-MCl2(dipeptideOR)2 (R = H, alkyl, SiMe3) (3) has been obtained. trans-Palladium complexes of type 3 and of type cis-Pd-Cl2(HisNHCHRCO2Et) (4) are also formed form the corresponding α-amino acid complexes and α-amino acid ester with a watersoluble carbodiimide.
    Notes: Der Chelatring von Platin(II)- und Palladium(II)-glycinat, cis-, trans-M(NH2CH2COO)2 (M = Pt, Pd), läßt sich mit Trialkylchlorsilanen unter Bildung der Dichlorobis(glycin-silylester)-Komplexe, cis-, trans-MCl2(NH2CH2CO2SiR3)2 (1), öffnen. Aus 1 oder den Komplexen MCl2(NH2CHRCO2H)2 werden mit Oxalylchlorid und DMF die α-Aminosäurechlorid-Verbindungen cis-, trans-MCl2(NH2CHRCOCl)2 (2) erhalten, welche mit N-(Trimethylsilyl)-α-aminosäureestern die Dipeptid-Komplexe cis-, trans-MCl2(DipeptidOR)2 (R = H, Alkyl, SiMe2) (3) liefern. trans-Palladium-Komplexe vom Typ 3 und vom Typ cis-PdCl2(His-NHCHRCO2Et) (4) entstehen auch aus den entsprechenden α-Aminosäure-Komplexen und dem α-Aminosäureester mit einem wasserlöslichen Carbodiimid.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 1417-1420 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes of Biologically Important Ligands, XLVI1.- Platinum (II) Complexes with Precursors of Unsaturated π-Amino Acidsα-Amino acid ester complexes cis-Cl2Pt(NH2CHRCO2Et)2 (R = H, Me, CH2CHMe2) react with tert-butyl hypochlorite to give N-chloro-α-amino acid ester complexes trans-Cl2Pt[NH(Cl)CHR-CO2Et]2. Dependent on the substituents 4-alkylidene-1,3-oxazolidine-2,5-dione is added to (Ph3P)2Pt(C2H4) by the C=C or the NH bond, respectively. The structure of the hydrido imido complex trans-(Ph3P)2(H)Pt— (4c) has been determined by X-ray analysis.
    Notes: Die α-Aminosäureester-Platinkomplexe cis-Cl2Pt(NH2CHRCO2-Et)2 (R = H, Me, CH2CHMe2) setzen sich mit tert-Butylhypochlorit zu den N-Chlor-α-aminosäureester-Verbindungen trans-Cl2Pt[NH(Cl)CHRCO2Et]2 um. 4-Alkyliden-1,3-oxazolidin-2,5-dion wird an (Ph3P)2Pt(C2H4) in Abhängigkeit von den Substituenten über die C—C-Doppel- oder die NH-Bindung addiert. Die Struktur des Hydrido-imido-Komplexes trans-(Ph3P)2(H)Pt—(4c) wurde durch Kristallstrukturanalyse bestimmt.
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  • 6
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 7
    ISSN: 0009-2940
    Keywords: Heterobimetallic complexes, alkyne-bridged ; Carbonyl complexes ; Molybdenum ; Tungsten ; Rhenium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrocarbon-Bridged Metal Complexes, XII.  -  Nucleophilic Addition of Carbonylmetallates to Cationic Alkyne Molybdenum Complexes: A Rational Way to Heterobimetallic Tetrahedranes MM′C2 (M = Mo, W; M′ = Re, Mn, Mo)The reactions of cationic alkyne complexes [Cp(L1)(L2)M(RC≡CR)]+ (L1 = CO, PR3, P(OMe)3; L2 = C2Me2, CO, P(OMe)3; M = Mo, W) with [Re(CO)5]- or [Mn(CO)5]- give heterobimetallic tetrahedranes Cp(OC)2M(μ2-η2:η2-RC≡CR)M′(CO)3L1 (M = Mo, W; M′ = Re, Mn) and Cp(OC)2Mo(μ2-η2:η2-MeC≡CMe)Re(CO)2[P(OMe)3]2. Similarly, the reaction of [Cp(OC)Mo(RC≡CR)2]+ or [Cp(Ph3P)(OC)Mo(RC≡CR)]+ with [CpW(CO)3]- provides a rational synthesis of Cp(OC)2Mo(μ2-η2:η2-RC≡CR)W(CO)2Cp. The dimetallatetrahedranes contain a semibridging CO group. The structures of Cp(OC)2Mo(μ2-η2:η2-H3CC≡CCH3)Re(CO)4 and Cp(OC)2Mo(μ2-η2:η2-H3CC≡CCH3)Re(CO)2[P(OMe)3]2 have been determined by X-ray crystallography.
    Notes: Die Umsetzung der kationischen Alkin-Komplexe [Cp-(L1)(L2)M(RC≡CR)]+ (L1 = CO, PR3, P(OMe)3; L2 = C2Me2, CO, P(OMe)3, M = Mo, W) mit [Re(CO)5]- oder [Mn(CO)5]- liefert die heterodimetallischen Tetrahedrane Cp(OC)2M(μ2-η2:η2-RC≡CR)M′(CO)3L1 (M = Mo, W;M′ = Re, Mn) und Cp(OC)2-(μ2-η2:η2-MeC≡CMe)Re(CO)2[P(OMe)3]2. Ebenso lassen sich in gezielter Weise aus [Cp(OC)Mo(RC≡CR)2]+ oder [Cp(Ph3P)-(OC)Mo(RC≡CR)]+ und [CpW(CO)3]- die Alkin-verbrückten Komplexe Cp(OC)2Mo(μ2-η2:η2-RC≡CR)W(CO)2Cp aufbauen. Die Dimetallatetrahedrane enthalten stets eine semiverbrückende CO-Gruppe. Die Strukturen von Cp(OC)2Mo(μ2-η2:η2-H3C-C≡CCH3)Re(CO)4 und Cp(OC)2Mo(μ2-η2:η2-H3CC≡CCH3)-Re(CO)2[P(OMe)3]2 wurden röntgenographisch bestimmt.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 3258-3267 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes with Biologically Important Ligands, XXXVIII. Complexes of Platinum(II), Palladium(II), Nickel(II), and Copper(II) with 1-Amino-1-cyclopropanecarboxylic Acid DerivativesMetal complexes with the anion of 1-amino-1-cyclopropanecarboxylic acid (2a - d), its ethyl ester (3a - c), with Schiff bases from this α-amino acid and amide acetal (4a - d), pyruvic acid (5a - d), and salicylaldehyde (6a - c, 7a,b), respectively, have been prepared. The compounds are characterized by their spectra. The X-ray structure analysis at -90°C of 3a shows nearly equal C - C bond lengths for the cyclopropane ring.
    Notes: Die Darstellung von Metallkomplexen mit dem Anion von 1-Amino-1-cyclopropancarbonsäure (2a - d), mit dessen Ethylester (3a - c), mit Schiff-Basen aus dieser α-Aminosäure und Amidacetal (4a - d), Brenztraubensäure (5a - d) und Salicylaldehyd (6a - c, 7a,b) wird beschrieben. Die Verbindungen werden spektroskopisch charakterisiert. Die bei -90°C durchgeführte Röntgenstrukturanalyse von 3a zeigt annähernd gleiche C - C-Abstände im Cyclopropanring.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 253-254 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of the 16-electron system Re(CO)+5 [as (OC)5ReFBF3] to acetylpentacarbonylchromate and -tungstate (as NMe+4[M(CO)5C(Me)O]-, M=Cr, W) leads to the acetyl-bridged complexes (OC)5M-C(Me)-O-Re(CO)5 (1a,b). This reaction is analogous to the classic synthesis of Fischer carbene complexes from acylcarbonylmetallates and oxonium salts and provides a further example for the isolobal concept. The chromium compound 1a has been characterized by single crystal X-ray diffraction analysis.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 1767-1769 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of Pentacarbonylrhenate to Coordinated Benzene:A δ,π-Bridged, Fluxional Cyclohexadienyl Complex, (OC)5Re-μ-(η1:η5-C6H6)Mn(CO)3Nucleophilic addition of pentacarbonylrhenate to coordinated benzene in [(η1:η5 -C6H6)Mn(CO)3]+ gives the η1:η5-cyclohexadienyl-bridged title compound 1. The structure of 1 has been determined by X-ray analysis. 1 is the first example of fluxional behaviour in η5-cyclohexadienyl complexes.
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