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  • Articles: DFG German National Licenses  (2)
  • Benzylideneacetone-copper complex  (1)
  • Fluxionality  (1)
  • 1
    ISSN: 1434-1948
    Keywords: Palladium ; Tripodal ligands ; O ligands ; Fluxionality ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [PdCl2(CH3CN)2] with the silver salt of the tripodal oxygen ligand L- = [(C5H5)Co{P(O)(OMe)2)}3]- yields the homoleptic oxygen ligand complex [PdL2] (1). The molecular structure of 1 was determined by single-crystal X-ray diffraction: monoclinic space group P21/n; a = 8.515(1), b = 13.627(2), c = 15.828(2) Å; β = 92.44(1)°; V = 1834.9(7) Å3; Z = 2. The complexes [Pd(PPh3)XL] [X = Cl (2a), Br (2b), I (2c)] have been prepared starting from 1. Complex 2a reacts with PPh3 to form [Pd(PPh3)2L]Cl (3a) and [Pd(PPh3)2L]L (3b). Treatment of 2a with CO in MeOH yields the carboxymethyl complex [{(PPh3)(COOMe)Pd(μ-Cl)}2] (4) and the protonated ligand HL. The carboxymethyl complex 4 shows some catalytic activity for the copolymerization of CO and ethene. Complex 4 reacts with AgL to yield [Pd(PPh3)(COOMe)L] (6). Alkylation of 2a with Me4Sn leads to the methyl complexes [Pd(PPh3)MeL] (7) and [Me2ClSnL] (8). CO insertion in the palladium-carbon bond of 7 gives the stable acetyl complex [Pd(PPh3){C(O)Me}L] (10). The palladium(II) complexes 1, 2, 3, 6, 7, and 10 of the tripodal oxygen ligand L are all fluxional molecules that have been studied by temperature-dependent 1H- and 31P-NMR spectroscopy.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2233-2240 
    ISSN: 0009-2940
    Keywords: Isonitrile complexes ; Copper-alkyne complexes ; Benzylideneacetone-copper complex ; Silver-carbonyl complex ; Oxygen tripod ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkene, Alkyne, Isonitrile, and Carbonyl Complexes of Copper(I) and Silver(I) with Tris-Chelating Oxygen LigandsThe preparation of η2-alkynecopper(I) complexes of the composition [LRCu(η2-alkyne)], alkyne = tolan, dimethyl acetylenedicarboxylate, is described. LR are anionic tris-chelating oxygen ligands of the type [(C5H5)Co{P(O)R2}3]-, R = OMe, OEt, O-i-Pr. The isonitrile complexes [LRM(CN—t-Bu)], M = Cu, Ag, have been prepared from [LOMeCu(CO)] and [{AgLOEt}2], respectively, The silver carbonyl complex [LOEt}Ag(CO)] [v(C≡O) = 2147 cm-1] forms in hexane and methanol solutions of [{AgLOEt}2] under 1 atm of CO gas. The olefin complexes [LRCu(ba)], ba = benzytlideneacetone, have been prepared from [Cu(CH3CN)4]PF6, NaLOMe, and ba and from the carbonyl complex [LOEtCu(CO)] and ba. The coordination of the carbon-carbon double bond of ba at the LRCu fragment does not lead to a 1,4-addition of methyllithium to the α,β-unsaturated ketone.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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