Cluster self-assembly of di[gold(I)]halonium cations

Schmidbaur, Hubert; Hamel, Armin; Mitzel, Norbert W.; Schier, Annette; Nogai, Stefan D.

doi:10.1073/pnas.062643599

Cited by 55 publications

(44 citation statements)

References 37 publications

(42 reference statements)

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“…+ SbF 6 À (5·SbF 6 ) (d = 28.5 ppm) [28] , and free 2-methyl-2-butene, which favors 5·SbF 6 and free alkene (Scheme 1). The thermal stability of the mixture presumably reflects the low equilibrium concentration of 3·SbF 6 present under these conditions.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Study of Cationic, Two‐Coordinate Triphenylphosphine– Gold–π Complexes

Brooner

Brown

Widenhoefer

2013

Chemistry A European J

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Cationic, two-coordinate triphenylphosphine-gold(I)-π complexes of the form [(PPh₃)Au(π ligand)]⁺SbF₆⁻ (π ligand=4-methylstyrene, 1∙SbF₆), 2-methyl-2-butene (3∙SbF₆), 3-hexyne (6∙SbF₆), 1,3-cyclohexadiene (7∙SbF₆), 3-methyl-1,2-butadiene (8∙SbF₆), and 1,7-diphenyl-3,4-heptadiene (10∙SbF₆) were generated in situ from reaction of [(PPh₃)AuCl], AgSbF₆, and π ligand at -78 °C and were characterized by low-temperature, multinuclear NMR spectroscopy without isolation. The π ligands of these complexes were both weakly bound and kinetically labile and underwent facile intermolecular exchange with free ligand (ΔG(≠) ≈9 kcal mol(-1) in the case of 6∙SbF₆) and competitive displacement by weak σ donors, such as trifluoromethane sulfonate. Triphenylphosphine-gold(I)-π complexes were thermally unstable and decomposed above -20 °C to form the bis(triphenylphosphine) gold cation [(PPh₃)₂Au]⁺SbF₆⁻ (2∙SbF₆).

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Section: Resultsmentioning

confidence: 99%

Synthesis and Study of Cationic, Two‐Coordinate Triphenylphosphine– Gold–π Complexes

Brooner

Brown

Widenhoefer

2013

Chemistry A European J

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“…[1][2][3][4] Intermolekulare Gold-Gold-Wechselwirkungen liegen wiederum in der Regel den Selbstorganisationsprozessen zugrunde. [2,5] Salze mit den vierkernigen Bis[triphenylphosphangold(I)]halonium-Dikationen A, [6,7] in denen vier Gold-Atome eine verzerrt-tetraedrische Anordnung mit vier relativ kleinen inter-und zwei größeren intramolekularen Au···Au-Abständen aufweisen, sind ungewöhn-liche Verbindungen dieses Typs, die ausschließlich im Festkörper stabil sind. Für das Bis(trigoldoxonium)-Dikation B [8] und den Bis(tetraauriomethan)-Komplex C [9] wurde ein analoger Aufbau ebenfalls nur im Festkörper beobachtet.…”

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Tetraedrische Gold(I)‐Cluster mit Carba‐closo‐dodecaboranylethinido‐Liganden: [{12‐(R₃PAu)₂CC‐closo‐1‐CB₁₁H₁₁}₂]

2011

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Im Festkörper und in Lösung dimerisieren die neutralen zweikernigen Gold(I)‐Komplexe [12‐(R3PAu)2CC‐closo‐1‐CB11H11] (R=Me, Et) zu vierkernigen Gold(I)‐Clustern. Für den Et3P‐Komplex wird in Lösung bei 25 °C ein Dimer‐Monomer‐Gleichgewicht beobachtet, während der Me3P‐Komplex auch bei 75 °C als Tetragold(I)‐Cluster vorliegt (siehe Struktur: C schwarz, B braun, P rosa, Au gelb).

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“…[8][9][10] Considering the halogen-pseudohalogen analogy, the question arises whether diauration of pseudohalide anions is also possible. In a first series of experiments it was shown that the diauration of the thiocyanate anion can indeed be achieved.…”

Section: X]mentioning

confidence: 99%

“…This effect is likely to reduce the attraction between the cations as recently demonstrated for other systems. [34] Isomeric mononuclear gold(i) thiocyanate complexes (R 3 P)AuSCN: For a realistic verification of the accuracy of the MP2/RDZ results, calculations at this level of theory were performed on mononuclear gold(i) thiocyanate complexes such as the hypothetical (H 3 P)AuSCN and the known (Me 3 P)AuSCN. These molecules are good reference compounds for this purpose, since 721 712 [b] CCSD(T) [30] 1.674 1.179 2091 2061 [c] 720 708 [c] exptl [31,32] 2066 [d] 745…”

Section: The Bis[(phosphine)gold(i)]chloronium Cationmentioning

confidence: 99%

Isomeric Mono‐ and Bis[(phosphane)gold(I)] Thiocyanate Complexes

Berger

Patzschke

Schneider

et al. 2005

Chemistry A European J

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The solid-state IR spectrum of Me(3)PAuSCN shows two signals in the range of the C-N stretching vibrations at 2075 and 2113 cm(-1). On the basis of thoroughly tested quantum chemical ab initio calculations (MP2 level of theory) these signals have been assigned to the two isomeric forms Me(3)PAuNCS and Me(3)PAuSCN. The molecular structures, the vibrational frequencies, and the relative energies of the two species have been calculated and the results compared with the experimental IR data. Treatment of Me(3)PAuSCN with equimolar quantities of [(Me(3)P)Au](+)[SbF(6)](-) in CH(2)Cl(2) at -78 degrees C gives the dinuclear reaction product [C(7)H(9)Au(2)NP(2)S](+)[SbF(6)](-) in high yields. A comparison of results of ab initio calculations and IR data suggest that at least three isomeric cationic species [(R(3)PAu)(2)NCS](+), [(R(3)PAu)(2)SCN](+) and [(R(3)PAu)SCN(AuPR(3))](+) are present, the second and third being the predominant components. The structures and vibrational frequencies of all three species have been calculated. The relative energies in the gas phase and in solution are discussed and compared with the corresponding data of the experimental IR spectra.

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Cluster self-assembly of di[gold(I)]halonium cations

Cited by 55 publications

References 37 publications

Synthesis and Study of Cationic, Two‐Coordinate Triphenylphosphine– Gold–π Complexes

Synthesis and Study of Cationic, Two‐Coordinate Triphenylphosphine– Gold–π Complexes

Tetraedrische Gold(I)‐Cluster mit Carba‐closo‐dodecaboranylethinido‐Liganden: [{12‐(R₃PAu)₂CC‐closo‐1‐CB₁₁H₁₁}₂]

Isomeric Mono‐ and Bis[(phosphane)gold(I)] Thiocyanate Complexes

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Cluster self-assembly of di[gold(I)]halonium cations

Cited by 55 publications

References 37 publications

Synthesis and Study of Cationic, Two‐Coordinate Triphenylphosphine– Gold–π Complexes

Synthesis and Study of Cationic, Two‐Coordinate Triphenylphosphine– Gold–π Complexes

Tetraedrische Gold(I)‐Cluster mit Carba‐closo‐dodecaboranylethinido‐Liganden: [{12‐(R3PAu)2CC‐closo‐1‐CB11H11}2]

Isomeric Mono‐ and Bis[(phosphane)gold(I)] Thiocyanate Complexes

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About

Tetraedrische Gold(I)‐Cluster mit Carba‐closo‐dodecaboranylethinido‐Liganden: [{12‐(R₃PAu)₂CC‐closo‐1‐CB₁₁H₁₁}₂]