2013
DOI: 10.1002/ange.201304820
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Isolierung neutraler mono‐ und dinuklearer Goldkomplexe von cyclischen Alkyl(amino)carbenen

Abstract: Das kleinste Stückchen Gold! Dank der Anwesenheit zweier cyclischer Alkyl‐(amino)carbene (CAACs) konnten Komplexe mit einem bzw. zwei Goldatomen in der formalen Oxidationsstufe 0 isoliert werden.

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Cited by 48 publications
(9 citation statements)
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References 77 publications
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“…Compound 3 was characterized by 1 H and 13 C NMR spectroscopy as well as by high‐resolution mass spectrometry. The 13 C NMR signal corresponding to the carbene carbon appears at 262.5 ppm, which is half‐way between those observed for gold(I) complexes 1 and 2 (237.4 and 230.4 ppm, respectively) and the recently reported neutral (CAAC menthyl )AuAu(CAAC menthyl ) complex17 (287.2 ppm), as is expected for a mixed‐valence gold(I)/gold(0) compound. Cluster 3 was found to be indefinitely stable in air and moisture both in the solid state and in solution; its melting point (240 °C (dec.)) is another indication of its high stability.…”
Section: Methodssupporting
confidence: 70%
See 1 more Smart Citation
“…Compound 3 was characterized by 1 H and 13 C NMR spectroscopy as well as by high‐resolution mass spectrometry. The 13 C NMR signal corresponding to the carbene carbon appears at 262.5 ppm, which is half‐way between those observed for gold(I) complexes 1 and 2 (237.4 and 230.4 ppm, respectively) and the recently reported neutral (CAAC menthyl )AuAu(CAAC menthyl ) complex17 (287.2 ppm), as is expected for a mixed‐valence gold(I)/gold(0) compound. Cluster 3 was found to be indefinitely stable in air and moisture both in the solid state and in solution; its melting point (240 °C (dec.)) is another indication of its high stability.…”
Section: Methodssupporting
confidence: 70%
“…19 Similar to the analogous cluster bearing P( o‐ Tol) 3 ligands,20 6 has a pseudo‐tetrahedral geometry, and can be viewed as three [CAAC‐Au] + units, with strong aurophilic interactions,21 bound to a central O 2− . In 7 , the AuAu distances (2.6324(8)–2.6706(8) Å) are much shorter than in 6 (3.1669(3)–3.3149(3) Å), which is indicative of true covalent bonds; for comparison, a gold–gold distance of 2.552 Å was observed for the neutral (CAAC)AuAu(CAAC) complex 17. In 9 , the distance between the two gold atoms bearing CAACs (2.6604(4) Å) is slightly longer than the other AuAu bonds (2.6191(4) and 2.6219(4) Å), arguing for the stronger σ‐donor properties of CAACs, compared to triphenyl phosphine 9…”
Section: Methodsmentioning
confidence: 87%
“…Compound 3 was characterized by 1 H and 13 C NMR spectroscopy as well as by high-resolution mass spectrometry. The 13 C NMR signal corresponding to the carbene carbon appears at 262.5 ppm, which is half-way between those observed for gold(I) complexes 1 and 2 (237.4 and 230.4 ppm, respectively) and the recently reported neutral (CAAC menthyl )AuÀAu(CAAC menthyl ) complex [17] (287.2 ppm), as is expected for a mixed-valence gold(I)/ gold(0) compound. Cluster 3 was found to be indefinitely stable in air and moisture both in the solid state and in solution; its melting point (240 8C (dec.)) is another indication of its high stability.…”
supporting
confidence: 67%
“…In 7, the AuÀAu distances (2.6324 (8)-2.6706(8) ) are much shorter than in 6 (3.1669(3)-3.3149 (3) ), which is indicative of true covalent bonds; for comparison, a gold-gold distance of 2.552 was observed for the neutral (CAAC)Au À Au-(CAAC) complex. [17] In 9, the distance between the two gold atoms bearing CAACs (2.6604 (4) ) is slightly longer than the other AuÀAu bonds (2.6191(4) and 2.6219(4) ), arguing for the stronger s-donor properties of CAACs, compared to triphenyl phosphine. [9] Owing to our ongoing interest in the gold-catalyzed functionalization of amines, [22] we chose to investigate the behavior of cluster 7 for the carbonylation of this class of compounds.…”
mentioning
confidence: 96%
“…[36][37][38] Attempts to obtain stable complexes of Au 2 were unsuccessful for along time, [39,40] until the group of Bertrand achieved the synthesis of ab is(carbene) complex in 2013. [41] Using their powerful CAAC ligands,s table,c rystalline complexes (CAAC)AuÀAu(CAAC)w ere obtained, and the molecular structures could be determined (Scheme 3, right: L = CAAC). Surprisingly,t he Au À Au distance was found to be 2.5520 long.Quantum-chemical calculations performed in this work (EDA-NOCV) resulted in Au À Au distances for the free Au 2 molecule and its complex of 2.546 and 2.579 , respectively,indicating aslight weakening of the AuÀAu bond upon complexation.…”
Section: Benchmark Data For Gold-gold Bonding Inmentioning
confidence: 99%