New Gold Clusters [Au8L6](BF4)2 and [(AuL)4](BF4)2 (L = P(mesityl)3)

Yang, Yi; Sharp, Paul R.

doi:10.1021/ja00094a082

Cited by 56 publications

(42 citation statements)

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“…A grand challenge to scientists in this field, however, is the precise determination of atomic structures of liganded gold clusters. To date, atomic structures of tens of liganded gold clusters have been determined via X-ray crystallography56789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960616263. Nevertheless, these revelations appear serendipitous as the structural determination largely hinges on availability of single crystals for the liganded gold clusters.…”

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A grand unified model for liganded gold clusters

et al. 2016

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A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three ‘flavours' (namely, bottom, middle and top) to represent three possible valence states. The ‘composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

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A grand unified model for liganded gold clusters

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“…In the 1990s, tetranuclear gold clusters [Au 4 (PR 3 ) 4 ]BF 4 (R ¼ t Bu [3] and (C 6 H 3 Me-1,3,5) [4]) were reported. Both clusters are synthesized from the corresponding oxonium salts [O{Au(PR 3 )] 3 ]BF 4 and [HO{Au(PR 3 )] 2 ]BF 4 (R ¼ t Bu and (C 6 H 3 Me-1,3,5)).…”

Section: Synthesis and Structural Characterization Of Phosphine-stabimentioning

confidence: 99%

“…The first is the cationic [Au 6 (PPh 3 ) 6 ] 2þ cluster, prepared through decomposition of the hydrazido complex [R 2 NN(AuPPh 3 ) 3 ]BF 4 [8] or through degradation of the cluster [Au 8 (PPh 3 ) 8 ] 2þ in the presence of [Ag(CN) 2 ] À [9]. The first is the cationic [Au 6 (PPh 3 ) 6 ] 2þ cluster, prepared through decomposition of the hydrazido complex [R 2 NN(AuPPh 3 ) 3 ]BF 4 [8] or through degradation of the cluster [Au 8 (PPh 3 ) 8 ] 2þ in the presence of [Ag(CN) 2 ] À [9].…”

Section: Synthesis and Structural Characterization Of Phosphine-stabimentioning

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Gold Nanomaterials

Fernndez¹,

Monge²

2008

Modern Supramolecular Gold Chemistry

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The strong development of activities related to the nanoscience and nanotechnology of gold has led to a great number of publications in this research field. In this chapter, we will focus on the synthesis of cluster aggregates displaying gold-gold bonds and the formation of gold nanoparticles. Special consideration will be given to the chemical bottom-up approach for the synthesis of gold nanomaterials using different methods.Section 3.2 describes the synthesis and structure of small gold clusters taking into account the number of gold atoms, the reducing agents employed and the stabilizing ligands used, such as phosphines, arsines, thiols, and so on. Section 3.3 discusses the synthesis and properties of large size gold clusters such as the Au 55 cluster series. Finally, in Section 3.4, we describe the synthesis of gold nanoparticles and the development of new nanomaterials based on gold nanoparticles using bottom-up chemical methods and give a short summary of their properties and applications. Molecular Gold ClustersHerein we describe the synthesis and characterization of small-size homonuclear gold cluster compounds with a nuclearity ranging from 3 to 39 gold atoms. These types of clusters are usually characterized through definitive structural techniques such as single-crystal X-ray diffraction, enabling in-depth study of the structural arrangements found in the solid state.This section is divided into two main subsections. The first describes the synthesis and characterization of phosphine-stabilized gold clusters. The second focuses on the synthesis and characterization of thiol-stabilized gold clusters and the study of other stabilizers such as arsines or boranes are described.The first tetranuclear gold clusters were reported in the 1980s, namely [Au 4 (PPh 3 ) 4 (m-I) 2 ] (Au-Au distances from 2.649(1) to 2.828(1) Å) [1] and [Au 4 (dppm) 3 (m 3 -I)I] (Au-Au distances from 2.724(1) to 2.947(1) Å) [2]. The first cluster was prepared through a degradation reaction of the nonanuclear cluster [Au 9 (PPh 3 ) 8 ] 3þ , while the second was obtained by reaction of the already mentioned [Au 4 (PPh 3 ) 4 (m-I) 2 ] cluster and one equivalent of dppm ligand. Both structures display distorted tetrahedral cores of gold atoms with the iodine atoms bridging two different gold centers in the first case and three gold centers in the second (Scheme 3.1).In the 1990s, tetranuclear gold clusters [Au 4 (PR 3 ) 4 ]BF 4 (R ¼ t Bu [3] and (C 6 H 3 Me-1,3,5) [4]) were reported. Both clusters are synthesized from the corresponding oxonium salts [O{Au(PR 3 )] 3 ]BF 4 and [HO{Au(PR 3 )] 2 ]BF 4 (R ¼ t Bu and (C 6 H 3 Me-1,3,5)). In both clusters, X-ray diffraction analysis showed that gold atoms form a regular tetrahedron and each phosphine ligand is coordinated to one gold center (Scheme 3.2).The latest examples of tetranuclear gold clusters are based on phosphinocarborane ligands, namely [Au 4 {(PPh 2 ) 2 C 2 B 9 H 10 } 2 {P(4-OMeC 6 H 4 ) 3 } 2 ] [5] and, more recently, [Au 4 {(PPh 2 ) 2 C 2 B 9 H 10 } 2 {PPh 3 } 2 ] [6]. The firs...

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“…Die Winkel PI -Aul-P2 und P3-Au2-P4 betragen 89.10(8) bzw. 86.51 (9)", sind also nahezu ideal, und die Atome P4-Au2-Au3 und P2-Aul-Au4 sind nahezu linear angeordnet (172.93 (6) Eingegangen am 6. November 1996 [Z 97361 Stichworte: Carborane -Cluster * Gold Angew.…”

Section: Verfahren [18] Auf Einem Pe-sciex-api-ili-tripel-quadrupol-munclassified