Organogold chemistry. XVII. Synthesis and reactions of the gold(I)-dimethylphosphonium-bis-methylid dimer

Schmidbaur, Hubert; Franke, R.

doi:10.1016/s0020-1693(00)90181-6

Cited by 87 publications

(39 citation statements)

References 18 publications

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“…Thus, its IR spectrum in Nujol mull shows, among others, absorptions at 1640 (vs) and 1190 cm À1 (vs) due to the tri-fluoroacetate anion, at 1501 (s), 961 (s), and 790 cm À1 (s) arising from the AuC 6 F 5 fragment, and at 580 cm À1 (w) characteristic of n(AuÀC ylide ). [22] The presence of the ylide ligand is also confirmed in the 1 H NMR spectrum, which displays a doublet at 2.03 ppm for the methylene group and a multiplet between 8.00 and 7.65 ppm corresponding to the aromatic protons. In addition, its 31 P{ 1 H} NMR spectrum shows a singlet at 31.7 ppm for the phosphorus atom of the ylide ligand.…”

Section: Resultsmentioning

confidence: 84%

Multiple Evidence for Gold(I)⋅⋅⋅Silver(I) Interactions in Solution

Fernández

Hardacre

Laguna

et al. 2009

Chemistry A European J

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[AuAg3(C6F5)(CF3CO2)3(CH2PPh3)]n (2) was prepared by reaction of [Au(C6F5)(CH2PPh3)] (1) and [Ag(CF3CO2)] (1:3). The crystal structures of complexes 1 and 2 were determined by X-ray diffraction, and the latter shows a polymeric 2D arrangement built by Au...Ag, Ag...Ag, and Ag...O contacts. The metallophilic interactions observed in 2 in the solid state seem to be preserved in concentrated THF solutions, as suggested by EXAFS, pulsed-gradient spin-echo NMR, and photophysical studies, which showed that the structural motif [AuAg3(C6F5)(CF3CO2)3(CH2PPh3)] is maintained under such conditions. Time-dependent DFT calculations agree with the experimental photophysical energies and suggest a metal-to-ligand charge-transfer phosphorescence process. Ab initio calculations give an estimated interaction energy of around 60 kJ mol(-1) for each Au...Ag interaction.

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Section: Resultsmentioning

confidence: 84%

Multiple Evidence for Gold(I)⋅⋅⋅Silver(I) Interactions in Solution

Fernández

Hardacre

Laguna

et al. 2009

Chemistry A European J

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“…With a single molar equivalent of halogen, gold(II) derivatives (eg X) are obtained (25)(26) therefore also neutral. The dimethyldiphenylphosphonium cation can undergo two deprotonation stages to give :CH 2PPh2CH 2 -, which can act simultaneously as a conventional cbonded ligand and as an ylide; however, the negative charge is delocalized, and this ligand forms symmetrical bridges: two such ligands bind to two gold atoms forming an eight-membered ring system (V; VI).…”

Section: Gold(l)mentioning

confidence: 99%

Organogold chemistry: I structure and synthesis

Parish

1997

Gold Bull

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“…18 We are interested in the versatility of metal-metal bond formations as well as their reaction mechanism in our heteronuclear tetranuclear system. Although metal-metal bond formations have been given by one-electron oxidation of each terminal metal in dinuclear complexes having no metal-metal bond, [19][20][21][22][23][24][25][26][27] comparable studies on multinuclear complexes composed of more than three transition metals are relatively rare. 5d,f Preliminary results obtained for the first synthesis of novel tetranuclear Rh-Mo-Mo-Rh arrays and oxidation of Rh(I) atoms to Rh(II) atoms, which induced formation of Rh-Mo bonds, were reported earlier, 28 and an extended and full account of the synthesis and reactivity of linearly aligned tetranuclear complexes bearing the M(I)‚‚‚ Mo(II)-Mo(II)‚‚‚M(I) skeleton (M ) Ir and Rh) is presented here.…”

Section: Introductionmentioning

confidence: 99%

Linear Metal−Metal-Bonded Tetranuclear M−Mo−Mo−M Complexes (M = Ir and Rh): Oxidative Metal−Metal Bond Formation in a Tetrametallic System and 1,4-Addition Reaction of Alkyl Halides

et al. 2007

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Reaction of Mo2(pyphos)4 (1) with [MCl(CO)2]2 (M = Ir and Rh) afforded linear tetranuclear complexes of a formula Mo2M2(CO)2(Cl)2(pyphos)4 (2, M = Ir; 3, M = Rh). X-ray diffraction studies confirmed that two "MCl(CO)" fragments are introduced into both axial sites of the Mo2 core in 1 and coordinated by two PPh2 groups in a trans fashion, thereby forming a square-planar geometry around each M(I) metal. Treatment of 2 and 3 with an excess amount of tBuNC and XylNC induced dissociation of the carbonyl and chloride ligands to yield the corresponding dicationic complexes [Mo2M2(pyphos)4(tBuNC)4](Cl)2 (5a, M = Ir; 6a, M = Rh) and [Mo2M2(pyphos)4(XylNC)4](Cl)2 (7, M = Ir; 8, M = Rh). Their molecular structures were characterized by spectroscopic data as well as X-ray diffraction studies of BPh4 derivatives [Mo2M2(pyphos)4(tBuNC)4](BPh4)2 (5b, M = Ir; 6c, M = Rh), which confirmed that there is no direct sigma-bonding interaction between the M(I) atom and the Mo2 core. The M(I) atom in 5 and 6 can be oxidized by either 2 equiv of [Cp2Fe][PF6] or an equimolar amount of I2 to afford Mo(II)2M(II)2 complexes, [Mo2M2(X)2(tBuNC)4(pyphos)4]2+ in which two Mo-M(II) single bonds are formed and the bond order of the Mo-Mo moiety has been decreased to three. The Ir(I) complex 5a reacted not only with methyl iodide but also with dichloromethane to afford the 1,4-oxidative addition products [Mo2Ir2(CH3)(I)(tBuNC)4(pyphos)4](Cl)2 (13) and [Mo2Ir2(CH2Cl)(Cl)(tBuNC)4(pyphos)4](Cl)2 (15), respectively, although the corresponding reactions using the Rh(I) analogue 6 did not proceed. Kinetic analysis of the reaction with CH3I suggested that the 1,4-oxidative addition to the Ir(I) complex occurs in an SN2 reaction mechanism.

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Organogold chemistry. XVII. Synthesis and reactions of the gold(I)-dimethylphosphonium-bis-methylid dimer

Cited by 87 publications

References 18 publications

Multiple Evidence for Gold(I)⋅⋅⋅Silver(I) Interactions in Solution

Multiple Evidence for Gold(I)⋅⋅⋅Silver(I) Interactions in Solution

Organogold chemistry: I structure and synthesis

Linear Metal−Metal-Bonded Tetranuclear M−Mo−Mo−M Complexes (M = Ir and Rh): Oxidative Metal−Metal Bond Formation in a Tetrametallic System and 1,4-Addition Reaction of Alkyl Halides

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