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  • 1
    ISSN: 0009-2940
    Keywords: M2P2 tetrahedral complexes ; Phosphido ligand complexes as intermediates ; Ni2P4O distorted prismane framework ; CO incorporation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes with Metal-Phosphorus Triple Bonds as Possible Intermediates in the Reactions between Chlorophosphinidenes and Metalates of Various Transition MetalsThe reaction of [{M′(CO)5}2PCl] (M′ = Cr, W) with various metalates ([Cp′Mo(CO)3]-, [Cp * Ni(CO)]-, [Cr2(CO)10]2-) yields the M2P2 tetrahedral complexes [(MLn)2(μ,η2- P2){M′(CO)5}2] (MLn = Cp*Ni, M′= Cr (1), W (2); MLn = Cp′Mo(CO)2, M′ = Cr (4); Cp* = η5-C5Me5, Cp* = η5C5H3tBu2) and the cyclo-P4 compound [{Cr(CO)4}(η4-P4){Cr(CO)5}4] 6. As side products the distorted prismane [(Cp*Ni)2{μ4,η4-(P2-O-P2)}{W(CO)5}2] 3 and the diphosphino-methanone complex [{Cp′Mo(CO)2}2{μ4η2-PC(O)P}-{Cr(CO)5}2] 5 are formed. The complexes are characterised by NMR, IR, MS, and X-ray structure analysis (1-5). Studying the reaction pathway provided evidence of phosphido intermediates of the type [LnM≡P→M′Ln].
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: P ligands ; P-P bond formation reaction ; Molybdenum ; Chromium ; Nickel ; Carbonyl complexes ; Main group elements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [Cr(CO)5PCl3] reacts with different metallates K[CpxMo(CO)3] [Cpx = ·5-C5H4tBu (Cp]), ·5-C5H3tBu2-1,3 (Cp))], K[CpFe(CO)2], K[Cp]Cr(CO)3], K[C}*Ni(CO)] and Na2[Cr2(CO)10] at -78°C in THF to yiel various P2, cyclo- P3 and cyclo-P5 ligand complexes of the formulae [Cp] Mo(CO)2 (.2-P3)] (1a), [Cp]Mo(CO)2(.3-P3)] (1b), [{CP'Mo-(CO)2}2(μ,.2-P2)] (2a), [{Cp]Mo(CO)2}2(μ, ·2-P2)] (2b), [Cp]Fe).5-P5)] (3), [(Cp'Cr)2(μ,.5-P5)] (4), [{Cp]Cr(CO)2}2-(μ,.2-P2)] (5), [(Cp*Ni)2(μ,.2-P2){Cr(CO)5}2] (6). [{(CO)5Cr}Cl2PPCl2{Cr(CO)5}] (7) and [{Cr(CO)5}2PCl (8). Comprehensive studies of the reaction pathway leading to formation of the cyclo-P3 product 1a give strong indications that a sequence involving metal-halogen exchange and stepwise P-P bond formation takes place, proceeding via [{CO}5Cr}Cl2PPCl2{Cr(CO)5}] (7) and the cyclo-P3 precursor compond [{Cp]Mo(CO)3}{Cp'Mo(CO)2}2{Cr(CO)5}(μ,.3:1:1-P3)] (9). The latter two complexes have been isolated and structurally characterized.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 63-71 
    ISSN: 0044-2313
    Keywords: diethyl triorganostannylmethyl N-acyl aminomalonates ; ethyl 3-(trimethylstannyl)-N-acyl alaninates ; 1,2-oxastannolane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: C-Stannylmethylated N-Acetyl- and N-Formyl-aminomalonic Acid DerivativesTin compounds of the type Me3SnCH2C(NHCOR) · (COOEt)2 (1: R = CH3; 2: R = H) are synthesized by reaction of acylaminomalonates with iodomethyl trimethylstannane. The halogenation of 1 and 2 yields the halostannylsubstituted compounds Me3-nXnSnCH2C(NHCOR)(COOEt)2 3-6 (R = Me, H; n = 1, 2; X = Cl, Br). The decarbethoxylation (KRAPCHO reaction) of 1 and 2 gives ethyl 3-(trimethylstannyl)-N-acyl alaninates (7 and 8). With one equivalent KOH 1 and 2 are transformed into the monoethyl malonates of the type Me3SnCH2C(NHCOR)(COOH)(COOEt) (9: R = CH3), which convert simultaneously under decarboxylation into 7 and 8 and by cyclisation under elimination of methane into the 1,2-oxastannolane derivatives 10 and 11. IR, NMR data and the determination of the crystal structure reveal for MeBr2SnCH2C(NHCOCH3)(COOEt)2 (5) hexacoordinated tin by intramolecular coordination of the amide-CO and one of the ester-CO groups.
    Notes: Zinnverbindungen des Typs Me3SnCH2C(NHCOR)(COOEt)2 (1: R = CH3; 2: R = H) werden durch Umsetzung von Acylaminomalonsäureestern mit Iodomethyltrimethylstannan dargestellt. Die Halogenierung von 1 und 2 liefert die halogenostannylsubstituierten Verbindungen Me3-nXnSnCH2C(NHCOR)(COOEt)2 3-6 (R = Me, H; n = 1, 2; X = Cl, Br). Die Decarbethoxylierung (KRAPCHO-Reaktion) von 1 und 2 führt zu 3-(Trimethylstannyl)-N-acyl-alaninethylestern (7 und 8). Mit einem Äquivalent KOH werden 1 und 2 in die Monoethylester des Typs Me3SnCH2C(NHCOR)(COOH)(COOEt) (9: R = CH3) überführt, die sich in Folgereaktionen sowohl unter Decarboxylierung zu 7 bzw. 8 als auch durch Cyclisierung unter Methanabspaltung zu den 1,2-Oxastannolanderivaten 10 bzw. 11 umwandeln. IR-, NMR-Daten und die Bestimmung der Kristallstruktur beweisen für MeBr2SnCH2C(NHCOCH3)(COOEt)2 (5) hexakoordiniertes Zinn durch intramolekulare Koordination der Amid-CO- sowie einer Ester-CO-Gruppe.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-2313
    Keywords: Cyanamidocarboxylate complexes ; IR ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pseudoelement Compounds VII. [1] Crystal and Molecular Structure of Tris(ethylenediamine)nickel(II)-bis(2-methyl-4-chlorophenoxy-cyanamidoacetate)Surprisingly, in the presence of ethylenediamine 2-methyl-4-chlorphenoxy-cyanamidoactetate reacts with nickel(II) and copper(II) ions preferentially under formation of complexes of the type [M(en)3]X2. The IR spectra and the X-ray diffraction investigations corresponding to [Ni(en)3][2-Me-ClC6H3OCH2C(O)NCN]2 show that two cyanamidocarboxylate ions [RC(O)NCN]- are bonded to the complex cation through, in each case, two N—H … O=C hydrogen bonds between NH protons of ethylenediamine ligands and the carbonyl oxygen atoms. Additionally, in the crystal weak N—H … N≡C bridges were found between the nitrile nitrogen atoms of the anions and NH protons of neighbouring complex cations.
    Notes: 2-Methyl-4-chlorphenoxy-cyanamidoacetat bildet zu unserer Überraschung mit Nickel(II)- und Kupfer(II)-Ionen in Gegenwart von Ethylendiamin bevorzugt Komplexe der Zusammensetzung [M(en)3]X2. IR-spektroskopische Messungen und die Kristallstruktrukturuntersuchung an [Ni(en)3][2-Me-4-ClC6H3OCH2C(O)NCN]2 zeigen, daß zwei Cyanamidocarboxylat-Anionen [RC(O)NCN]- über jeweils zwei N—H … O=C-Wasserstoffbrückenbindungen zwischen N—H-Protonen der Ethylendiamin-Liganden und den Carbonyl-Sauerstoffatomen an ein komplexes Kation [Ni(en)3]2+ gebunden sind. Im Kristall liegen außerdem noch schwache N—H … N≡C-Brücken zwischen Nitril-N-Atomen der Anionen und NH-Protonen benachbarter komplexer Kationen vor.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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