Synthesis and X-ray characterization of an iodine-bridged tetranuclear gold cluster, di-µ-iodo-tetrakis(triphenylphosphine)-tetrahedro-tetragold

Demartin, Francesco; Manassero, Mario; Naldini, L.; Ruggeri, Ruggero; Sansoni, Mirella

doi:10.1039/c39810000222

“…[15] On the basis of these findings and in agreement with the situation in Au 3 In 3 clusters, an oxidation state of zero can be considered for the gold atoms in 2 and 3. [13,14] Quantum-chemical calculations [16] have been carried out for the anion of 2.…”

supporting

confidence: 64%

GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry

Hagen

¹

,

Pantenburg

²

,

Weigend³

et al. 2003

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We are currently investigating the coordination chemistry and ligand properties of the dianionic stanna-closo-dodecaborate cluster [SnB 11 H 11 ] 2À (1). So far, in a variety of transition-metal complexes, the ligand was found to coordinate exclusively as a terminal ligand with the formation of a tin-metal bond.[1]Here we present the surprising results of preliminary investigations on the stannaborate chemistry with gold electrophiles. 2À :[(Ph 3 P)AuCl]). Interestingly, 50 % of the starting material [(Ph 3 P)AuCl] is still present in the mixture. The other signals in the 31 P NMR spectrum exhibit tin satellites, which provides direct spectroscopic evidence for the formation of a covalent Au À Sn bond. In this solution the anion of 3 is the major Au-Sn component (35 %) and exhibits a characteristic signal in the 31 P NMR spectrum at d = 54.4 ppm with a 2 J(Sn,P) coupling constant of 109.4 Hz. The anion of 2 was identified in solution by a small signal (3 %) at d = 62.9 ppm ( 2 J(Sn,P) = 186.9 Hz). A bis(triphenylphosphane) substitution product ([(Ph 3 P) 2 Au(SnB 11 H 11 )] À ) is also present in solution (5 %) and displays a signal in the 31 P NMR spectrum at d = 44.5 ppm ( 2 J(P, 117 Sn) = 984.2 Hz, 2 J(P, 119 Sn) = 1027.5 Hz). This compound was synthesized in a separate experiment from nucleophile 1, PPh 3 , and [(Ph 3 P)AuCl] in reasonable yield and details will be published later. Treatment of the [(Ph 3 P)AuCl] with 1.5 equivalents of heteroborate 1, led to an increase in the amount of Au 2 Sn 3 cluster 3 formed (68.6 % yield).The geometry of the metal core in the anions of 2 (Figure 1) and 3 (Figure 2)

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“…In them, what is really important is the number of valence electrons, rather than the number of atoms. [74] Electron shell closing has also been found in some ligandprotected nanoclusters, for example, 8e in [Au 25 (SR) 18 ] À , [76] 58e in [Au 102 (SR) 44 ], and 34e in [Au 68 (SR) 34 ] [77] (identified in MALDI-MS). But there are many nanoclusters that do not conform to the electron shell closing numbers, include neutral [Au 25 (SR) 18 ] (7e), [78] [Au 38 (SR) 24 ] (14e), [59] [Au 144 (SR) 60 ] (84e), [65] [Au 20 (SR) 16 ] (4e), [79] [Au 24 (SR) 20 ] (4e), [80] [Au 40 (SR) 24 ] (16e), [81] etc.…”

Section: Structural and Electronic Evolutionmentioning

confidence: 94%

Quantum‐Sized Gold Nanoclusters: Bridging the Gap between Organometallics and Nanocrystals

Jin

¹

,

Zhu

²

,

Hu

³

2011

Chemistry A European J

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This Concept article provides an elementary discussion of a special class of large-sized gold compounds, so-called Au nanoclusters, which lies in between traditional organogold compounds (e.g., few-atom complexes, <1 nm) and face-centered cubic (fcc) crystalline Au nanoparticles (typically >2 nm). The discussion is focused on the relationship between them, including the evolution from the Au⋅⋅⋅Au aurophilic interaction in Au(I) complexes to the direct Au-Au bond in clusters, and the structural transformation from the fcc structure in nanocrystals to non-fcc structures in nanoclusters. Thiolate-protected Au(n)(SR)(m) nanoclusters are used as a paradigm system. Research on such nanoclusters has achieved considerable advances in recent years and is expected to flourish in the near future, which will bring about exciting progress in both fundamental scientific research and technological applications of nanoclusters of gold and other metals.

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“…Formally, we find Au I in clusters 2 and 3 , but the AuAu bond lengths are shorter than the discussed values for Au I –Au I interactions (275–325 pm) 12. In both 2 and 3 the P‐Au‐Au‐P axis is linear, and this geometry together with the short AuAu bonds can be compared with those in the heteroatomic gold clusters [(dppe) 2 Au 3 In 3 Cl 6 (thf) 3 ] (dppe=1,2‐bis(diphenylphosphanyl)ethane),13 [(dppe) 2 Au][(dppe) 2 Au 3 In 3 Br 7 (thf)],14 [Au 4 (PPh 3 ) 4 (μ 2 ‐SnCl 3 ) 2 ],5 [Au 2 Pt 2 (PPh 3 ) 4 (CN‐xylyl) 4 ],2 and [Au 4 (PPh 3 ) 4 (μ 2 ‐I) 2 ] 15. On the basis of these findings and in agreement with the situation in Au 3 In 3 clusters, an oxidation state of zero can be considered for the gold atoms in 2 and 3 13.…”

Section: Methodsmentioning

confidence: 99%

GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry

Hagen

¹

,

Pantenburg

²

,

Weigend³

et al. 2003

View full text Add to dashboard Cite

We are currently investigating the coordination chemistry and ligand properties of the dianionic stanna-closo-dodecaborate cluster [SnB 11 H 11 ] 2À (1). So far, in a variety of transition-metal complexes, the ligand was found to coordinate exclusively as a terminal ligand with the formation of a tin-metal bond.[1]Here we present the surprising results of preliminary investigations on the stannaborate chemistry with gold electrophiles. 2À :[(Ph 3 P)AuCl]). Interestingly, 50 % of the starting material [(Ph 3 P)AuCl] is still present in the mixture. The other signals in the 31 P NMR spectrum exhibit tin satellites, which provides direct spectroscopic evidence for the formation of a covalent Au À Sn bond. In this solution the anion of 3 is the major Au-Sn component (35 %) and exhibits a characteristic signal in the 31 P NMR spectrum at d = 54.4 ppm with a 2 J(Sn,P) coupling constant of 109.4 Hz. The anion of 2 was identified in solution by a small signal (3 %) at d = 62.9 ppm ( 2 J(Sn,P) = 186.9 Hz). A bis(triphenylphosphane) substitution product ([(Ph 3 P) 2 Au(SnB 11 H 11 )] À ) is also present in solution (5 %) and displays a signal in the 31 P NMR spectrum at d = 44.5 ppm ( 2 J(P, 117 Sn) = 984.2 Hz, 2 J(P, 119 Sn) = 1027.5 Hz). This compound was synthesized in a separate experiment from nucleophile 1, PPh 3 , and [(Ph 3 P)AuCl] in reasonable yield and details will be published later. Treatment of the [(Ph 3 P)AuCl] with 1.5 equivalents of heteroborate 1, led to an increase in the amount of Au 2 Sn 3 cluster 3 formed (68.6 % yield).The geometry of the metal core in the anions of 2 (Figure 1) and 3 (Figure 2)

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Synthesis and X-ray characterization of an iodine-bridged tetranuclear gold cluster, di-µ-iodo-tetrakis(triphenylphosphine)-tetrahedro-tetragold

Abstract: The role played by the phosphine ligands in determining strong linear gold-gold and gold-phosphine bonding has been discussed

Cited by 57 publications

References 0 publications

GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry

GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry

Quantum‐Sized Gold Nanoclusters: Bridging the Gap between Organometallics and Nanocrystals

GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry

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Synthesis and X-ray characterization of an iodine-bridged tetranuclear gold cluster, di-µ-iodo-tetrakis(triphenylphosphine)-tetrahedro-tetragold

Abstract: The role played by the phosphine ligands in determining strong linear gold-gold and gold-phosphine bonding has been discussed

Cited by 57 publications

References 0 publications

GoldGold Interaction—Stannaborate [SnB11H11]2− Coordination Chemistry

GoldGold Interaction—Stannaborate [SnB11H11]2− Coordination Chemistry

Quantum‐Sized Gold Nanoclusters: Bridging the Gap between Organometallics and Nanocrystals

GoldGold Interaction—Stannaborate [SnB11H11]2− Coordination Chemistry

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Product

Resources

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GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry

GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry

GoldGold Interaction—Stannaborate [SnB₁₁H₁₁]²⁻ Coordination Chemistry