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  • 1
    Electronic Resource
    Electronic Resource
    Metallkomplexe funktioneller Isocyanide, XVI1) 1,3-Dipolare Cycloadditionen von Heteroallenen an die metallorganischen Nitrilylide [(OC)5M—C≡N—CHR]- (M = Cr, W; R = CO2Et) (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 2031-2040 
    Details
    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 Functional Isocyanides, XVI1). - 1,3-Dipolar Cycloadditions of heteroallenes to the Organometallic Nitrile Ylides [(OC)5M—C≡N—CHR]- (M = Cr, W; R = CO2Et)In the presence of bases (NEt3, KtBuO, LinBu), the isocyanoacetic ester ligand in M(CO)5CNCH2CO2Et (M = Cr, W, 2,3) reacts with the heteroallenes PhN=C=O and PhN=C=S regio- and site-selectively to give the carbenoid heterocyclic ligands {:CN(H)-C(CO2Et)C(X-)NPh }- (X = O, S; 6,7, 13, 14). The exocyclic olate and thiolate functions have been alkylated and acylated (8-10, 15), while the latter has also been oxidized to give the disulfide 16. [M{CN(H)C(CO2Et)C(S-)NPh }(CO)5]- (M = Cr, W), moreover, has been introduced into the platinum complexes PtCl2(PEt3)2 and [PtCl(PPh3)2]2(BF4)2 where it acts as a monodentate ligand coordinating with its exo-sulfur atom (17-19). The structural assignments are made on the basis of IR, NMR (1H, 13C, 31P) and mass spectroscopy data as well as of an X-ray structure analysis of NEt3H-[W {CN(H)C(CO2Et)C(O-NPh }(CO)5] (7). In the solid state strong hydrogen bonding occurs both between the and the exocyclic olate function of the anion, and between the NH and O=C(ester) groups of two complexes with formation of almost discrete dimers.
    Notes: Der Isocyanessigester-Ligand in M(CO)5CNCH2CO2Et (M = Cr, W, 2,3) reagiert in Gegenwart von Basen (NEt3, KtBuO, LinBu) mit den Heteroallenen PhN=C=O und PhN=C=S regio- und seitenselektiv zu den carbenoiden Heterocyclenliganden {:CN(H)-C(CO2Et)C(X-)NPh }- (X = O, S; 6,7, 13, 14). Die exocylischen Olat- und Thiolatfunktionen lassen sich alkylieren und acylieren (8-10, 15) bzw. zum Disulfid 16 oxidieren. Darüber hinaus wird [M{CN(H)C(CO2ET)C(S-)NPh }C(CO)5]- (M = Cr, W) als einzähniger, über das exo-Schwefelatom koordinierender Ligand in die Platinkomplexe PtCl2(PEt3)2 und [PtCl(PPh3)2]2(BF4)2 eingebaut (17-19). Die Strukturzuweisungen erfolgen auf der Basis von IR-, Kernresonanz (1H, 13C, 31P)- und massenspektroskopischen Daten, sowie der Röntgenstrukturanalyse von NEt3H-[W{CN(H)C(CO2Et)C(O-)NPh }(CO)5] (7). Im Festkörper liegen starke H-Brücken sowohl zwischen Kation und exocyclischer Olat-Funktion des Anions, als auch zwischen den NH- und O=C(Ester)-Gruppierungen je zweier Komplexanionen vor, so daß nahezu diskrete Dimere resultieren.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871201215
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  • 2
    Electronic Resource
    Electronic Resource
    Metallkomplexe funktioneller Isocyanide, XI. Homoleptische Carbenkomplexe, II. Tetrakis(oxazolidin-2-yliden)- und Tetrakis(perhydrooxazin-2-yliden)nickel, -palladium und -platin (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2235-2254 
    Details
    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 Functional Isocyanides, XI. Homoleptic Carbene Complexes, II. Tetrakis(oxazolidin-2-ylidene)- and Tetrakis(perhydrooxazin-2-ylidene)nickel, -palladium, and -platinumThe compounds MX2 (X = Cl, Br, I, ClO4) and MX2L2 (L = MeCN, PhCN, PPh3) of the nickel triad react with the (2- and 3-hydroxyalkyl)isocyanides CNCHRCHR′OH (R = R′ = H; R = Et, R′ = H; R = H, R′ = Me) and CNCH2CH2CH2OH to give the stable water-soluble tetracarbene complexes (3a - c, 4a - c, 5a - c, 15a - c, 22a, b) and (3d - 5d, 15d), the anions of which can be exchanged for e.g. BF4-, BPh4- or [PdI4]2-. In some cases, also mixed complexes (e.g. Pd{CN4 (7d), (20)) are obtained. According to spectroscopic (13C NMR, UV) and X-ray structural data (of (5a)), the carbene complexes are to be regarded as C-metalated but not metal-stabilized oxazolinium species. The four five-membered rings are almost perpendicular with respect to the PdC4 coordination plane. The complex dication and two chloride anions are strongly NH…Cl-bonded while further linkage occurs through weaker CH…Cl and weak CH…O hydrogen bridge bonding.
    Notes: Die Metallverbindungen MX2 (X = Cl, Br, I, ClO4) und MX2L2 (L = MeCN, PhCN, PPh3) der Nickeltriade reagieren mit den (2- und 3-Hydroxyalkyl)isocyaniden CNCHRCHR′OH (R = R′ = H;R = Et, R′ = H;R = H,R′ = Me) und CNCH2CH2CH2OH zu den stabilen wasserlöslichen Tetracarben-Komplexen 3a - c, 4a - c, 5a - c. 15a - c, 22a, b) und 3d - 5d, 15d), deren Anionen z. B. gegen BF4-, BPh4- oder [PdI4]2- austauschbar sind. In einigen Fällen werden auch gemischte Komplexe (z. B. Pd{CN4- (7d), (20)) erhalten. Spektro-skopischen (13C-NMR, UV) wie Röntgenstrukturdaten (von (5a)) zufolge sind die Carbenkomplexe als C-metallierte, aber nicht metallstabilisierte Oxazolinium-Spezies aufzufassen. Die vier Liganden-Fünfringe stehen auf der PdC4-Koordinationsebene angenähert senkrecht. Zwischen dem Komplex-Dikation und zwei Chlorid-Anionen bestehen starke NH…Cl-, zu weiteren Kationen schwächere CH…Cl- und schwache CH…O-Wasserstoff-brückenbindungen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180608
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