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  • Inorganic Chemistry  (3)
  • Azido bridge  (1)
  • Wiley-Blackwell  (4)
  • 1995-1999  (4)
  • 1
    ISSN: 0009-2940
    Keywords: Gold complexes ; Silver complexes ; Palladium complexes ; S-Donor ; Thiones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: AgClO4 reacts with bidentate ligands 2-(methylthio)pyridine (SMepy) or complexes PPN[Au(Spy)2] [PPN = N(PPh3)2, HSpy = pyridine-2(1H)-thione) or PPN[Au(Sbz)2] (HSbz = benzoxazole-2(3H)-thione), themselves acting as ligands, to give dinuclear complexes [Ag2(μ-SMepy)2](ClO4)2 (1), [AgAu(μ-Spy)2] (2), or [AgAu(μ-Sbz)2] (3), respectively. By treating 1 with [AuCl(tht)] (tht = tetrahydrothiophene), [Au(SMepy)(tht)]ClO4 (4) is obtained which, in turn, reacts with SMepy to give [Au(SMepy)2]ClO4 (5). Similarly, [PdCl2(NCPh)2] reacts with SMepy in 1:1 molar ratio to give [Pd2Cl2(μ-Cl)2(SMepy)2] (6) which reacts with SMepy in 1:2 molar ratio to give [PdCl2(SMepy)2] (7). On the other hand, HSpy reacts with Ag2CO3 to give [Ag2(μ-Spy)2] (8), and (SMepyH)ClO4 reacts with [Au(acac)PPh3] (acacH = acetyl-acetone) to give [Au(SMepy)PPh3]ClO4 (9).
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  • 2
    ISSN: 0009-2940
    Keywords: Gold ; Mercury ; Nitroaryl ; Transmetallation ; Biaryl ; C-C Coupling ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Butoxynitrobenzene reacts with [Hg(O2CCF3)2] and LiCl to give [Hg(R)Cl] [R = C6H3NO2-3, OnBu-6 (1)] which is symmetrized by Me4NCl to give [HgR2] (2), the crystal structure of which has been determined. The reaction of 2 with Me4N[AuCl4] affords Me4N[Au(R)Cl3] (3) by a facile transmetallation process. Complex 3 reacts with PPh3 (1:1) to give cis-[Au(R)(PPh3)Cl2] (4). The diaryl complex [-Ph-2)(R)Cl] (5) is obtained by reaction of 3 with [Hg-(C6H4N=NPh-2)2] through a second transmetallation reaction. Complex 5 and PPh3 (1:1) give [AuClPPh3] and the C-C coupling biphenyl RC6H4N=NPh-2 (6).
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  • 3
    ISSN: 0009-2940
    Keywords: Synthesis aryl complexes of gold(III) ; Mercury(II) as transmetallating agent ; X-ray crystal structure ; Ketonylgold(III) complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formylarylmercury(II) complex [Hg{C6H(CHO)-6-(OMe)3-2,3,4}2] reacts with 4-butylaniline (1:2) to give [Hg{C6H(CH=NC6H4C4H9-4′)-6-(OMe) 3-2,3,4}2] (1) by a condensation reaction. This complex reacts with Me4-N[AuCl4] (1:1) to give [Hg{C6H(CH=NC6H4C4H9-4′)-6-(OMe) 3-2,3,4}Cl] (2) and the monoarylgold(III) compound cis-C6H4-nBu-4′)-6-(OMe)3-2,3,4}Cl2] (3). This complex reacts with PPh3 (1:1) to give the adduct cis-[Au{C6H(CH=NC6H4-n, Bu-4′)-6-(OMe)3-2,3,4}Cl2(PPh3)] (4) and with AgClO4 (1:1) in acetone to give the ketonyl complex cis-[C6H4-nBu-4′)-6- (OMe)3-2,3,4}-{CH2C(O)Me}Cl] (5). cis-Me4N[Au(C6H4NO2-2)2Cl 2] react with [Hg{C6H3(N=NC6H4OMe-4′)-2-(OMe)-5}Cl] and Me4NCl (1:1:1) to give cis-[C6H4OMe-4′)-2- (OMe)-5}(C6H4NO2-2)2] (6): Similarly, cis-Me4N-[Au(C6H4CF3-2)2 Cl2] (7), obtained by treating [Hg(C6H4CF3-2)2] with Me4N[AuCl4] and Me4NCl (1:1:1), reacts with [Hg(C6H4CH2NMe2-2)Cl] and Me4NCl (1:1:1) to give the triarylgold(III) complex cis-[Me2-2)(C6H4CF3-2)2] (8). This complex can also be obtained by treating cis-[Me2-2)Cl2] with [Hg(C6H4CF3-2)2] and Me4NCl (1:1:1). The crystal structure of 3 reveals the presence of two independent molecules, in one of which the butylphenyl group is disordered. The geometry at the gold atom is square planar; distortions may be attributed to the narrow bite angle and steric repulsion between a chloride ligand and the ortho-methoxy group. The greater trans influence of the aryl ligand causes a great difference in Au-Cl bond lengths.
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  • 4
    ISSN: 1434-1948
    Keywords: Bridging ligands ; Manganese ; Azido bridge ; Alternating chain ; Magnetic properties ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ligands 3-ethyl-4-methylpyridine (3-Et,4-Mepy) and azide coordinate to MnII forming an alternating chain with the formula [Mn(3-Et,4-Mepy)2(μ-N3)2]n. This compound crystallizes in the space group P-1. The compound consists of chains of octahedrally coordinated manganese atoms alternately bridged by double end-to-end (μ1,3) and double end-on (μ1,1) azido bridges, which results in a structurally and magnetically alternating chain. The 3-ethyl-4-methylpyridine ligands are arranged trans, completing the six-fold coordination spheres of the manganese atoms. The Mn-Mn distances are distinctly different: Mn(1)-Mn(1A) = 5.149(3) Å (double end-to-end azido bridge) and Mn(1)-Mn(1B) = 3.402(2) Å (double end-on azido bridge). The magnetic properties of the compound, as studied in the temperature range 300-4 K, show bulk antiferromagnetic interaction. Fitting of the magnetic data by using an equation for alternating ferro-antiferromagnetic S = 5/2 1-D systems gives the parameters JAF = -13.7(1) cm-1, JF = 2.4(1) cm-1, g = 2.036(2).
    Additional Material: 2 Ill.
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