Au70S20(PPh3)12: an intermediate sized metalloid gold cluster stabilized by the Au4S4 ring motif and Au-PPh3 groups

Kenzler, Sebastian; Schrenk, Claudio; Frojd, Andrew R.; Häkkinen, Hannu; Clayborne, Andre; Schnepf, Andreas

doi:10.1039/c7cc08014j

Cited by 40 publications

(39 citation statements)

References 40 publications

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Section: Resultssupporting

confidence: 73%

“…This shows that LiSTsi not only acts as as ource of the substituent but also as ad onor of sulfur atoms and oxidant of the germanium atoms.T his ability of LiSTsi was also recently observed during the synthesis of the giant metalloid gold clusters Au 108 S 24 (PPh 3 ) 16 [16] and Au 70 S 20 (PPh 3 ) 12 . [17] Compound 3 was obtainedascolorless crystals out of apentane extract. Recrystallization from toluene at À28 8Cg ave 3 in 86 %y ield.…”

Section: Resultsmentioning

confidence: 99%

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Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

Kunz

Schrenk

Schnepf

2019

Chemistry A European J

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The reaction system GeCl2⋅dioxane/LiSTsi (Tsi=C(SiMe3)3) opens a fruitful area in germanium chemistry, depending on the stoichiometry and solvent used during the reaction. For example, the reaction of GeCl2⋅dioxane in toluene with two equivalents of the thiolate gives the expected germylene Ge(STsi)2 in excellent yield. This germylene readily reacts with hydrogen and acetylene, however, in a non‐selective way. By using an excess amount of the thiolate and toluene as the solvent, the germanide [Ge(STsi)3][Li(thf)] is obtained. Performing the same reaction in thf leads to a C−H activation of thf to give (H7C4O)Ge[STsi](μ2‐S)2Ge[STsi]2, in which the thf molecule is still intact. Using a sub‐stoichiometric amount of the thiolate leads to the heteroleptic compound [ClGe(STsi)]2 and to the insertion product (thf)Ge[S‐GeCl2‐Tsi]2, in which additional GeCl2 molecules insert into the C−S bonds of Ge(STsi)2. The synthesis and the experimentally determined structures of all compounds are presented together with first reactivity studies of Ge(STsi)2.

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Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

Kunz

Schrenk

Schnepf

2019

Chemistry A European J

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“…Due to the distinct charge distribution in Au 21 hcp and Au 21 fcc , it is expected that the electronic states of these two clusters will be critically different . This assumption is verified by the analysis of HOMOs, LUMOs, and HOMO–LUMO gap from the partial density of states (PDOS) of Dmol3 calculation.…”

Section: Resultsmentioning

confidence: 80%

“…[61] Due to the distinct charged istribution in Au 21 hcp and Au 21 fcc , it is expected that the electronic states of these two clusters will be critically different. [62] This assumption is verifiedb yt he analysiso fH OMOs, LUMOs, and HOMO-LUMO gap from the partial density of states (PDOS) of Dmol3 calculation. In PDOS analysiso fb oth Au 21 hcp and Au 21 fcc (Figure 4), the total clusters are divided into three parts, the sum of all Au core atoms (denoted as Au core in Figure 4), the Au stap S stap part including all staple atoms (denoted as (AuS) stap ), and the sum of S bri atoms (denoted as S bri ).…”

Section: Ta Ble 2s Hows the Hirshfeldc Hargea Nalysiso Fd Ifferent Tymentioning

confidence: 84%

The Structure–Property Correlations in the Isomerism of Au₂₁(SR)₁₅ Nanoclusters by Density Functional Theory Study

Bai

Weng

et al. 2019

Chemistry An Asian Journal

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Isomerism of atomically precise noble metal nanoclusters provides an excellent platform to investigate the structure–property correlations of metal nanomaterials. In this study, we performed density functional theory (DFT) and time‐dependent (TD‐DFT) calculations on two Au21(SR)15 nanoclusters, one with a hexagonal closed packed core (denoted as Au21hcp), and the other one with a face‐centered cubic core (denoted as Au21fcc). The structural and electronic analysis on the typical Au–Au and Au–S bond distances, bond orders, composition of the frontier orbitals and the origin of optical absorptions shed light on the inherent correlations between these two clusters.

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“…A large metalloid Au 108 S 24 (PPh 3 ) 16 cluster with 24 µ 3 -S has been revealed, which consists of an octahedral Au 44 core, an Au 48 S 24 shell and 16 Au(PPh 3 ) elements [20]. Very recently, Kenzler et al has synthesized an intermediate size metalloid gold cluster Au 70 S 20 (PPh 3 ) 12 , revealing an Au 22 core surrounded by the Au 48 S 20 (PPh 3 ) 12 shell [21]. According to their report, Au 4 S 4 unit is a central structural motif in the shell and they suggest that they could not elucidate a definite superatom character or distinct shell structure in the cluster.…”

Section: Introductionmentioning

confidence: 99%

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

Tian

Cheng

2019

Nanomaterials

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In order to increase the understanding of the recently synthesized Au70S20(PPh3)12 cluster, we used the divide and protect concept and superatom network model (SAN) to study the electronic and geometric of the cluster. According to the experimental coordinates of the cluster, the study of Au70S20(PPh3)12 cluster was carried out using density functional theory calculations. Based on the superatom complex (SAC) model, the number of the valence electrons of the cluster is 30. It is not the number of valence electrons satisfied for a magic cluster. According to the concept of divide and protect, Au70S20(PPh3)12 cluster can be viewed as Au-core protected by various staple motifs. On the basis of SAN model, the Au-core is composed of a union of 2e-superatoms, and 2e-superatoms can be Au3, Au4, Au5, or Au6. Au70S20(PPh3)12 cluster should contain fifteen 2e-superatoms on the basis of SAN model. On analyzing the chemical bonding features of Au70S20(PPh3)12, we showed that the electronic structure of it has a network of fifteen 2e-superatoms, abbreviated as 15 × 2e SAN. On the basis of the divide and protect concept, Au70S20(PPh3)12 cluster can be viewed as Au4616+[Au12(µ3-S)108−]2[PPh3]12. The Au4616+ core is composed of one Au2212+ innermost core and ten surrounding 2e-Au4 superatoms. The Au2212+ innermost core can either be viewed as a network of five 2e-Au6 superatoms, or be considered as a 10e-superatomic molecule. This new segmentation method can properly explain the structure and stability of Au70S20(PPh3)12 cluster. A novel extended staple motif [Au12(µ3-S)10]8− was discovered, which is a half-cage with ten µ3-S units and six teeth. The six teeth staple motif enriches the family of staple motifs in ligand-protected Au clusters. Au70S20(PPh3)12 cluster derives its stability from SAN model and aurophilic interactions. Inspired by the half-cage motif, we design three core-in-cage clusters with cage staple motifs, Cu6@Au12(μ3-S)8, Ag6@Au12(μ3-S)8 and Au6@Au12(μ3-S)8, which exhibit high thermostability and may be synthesized in future.

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Au₇₀S₂₀(PPh₃)₁₂: an intermediate sized metalloid gold cluster stabilized by the Au₄S₄ ring motif and Au-PPh₃ groups

Cited by 40 publications

References 40 publications

Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

The Structure–Property Correlations in the Isomerism of Au₂₁(SR)₁₅ Nanoclusters by Density Functional Theory Study

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

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Au70S20(PPh3)12: an intermediate sized metalloid gold cluster stabilized by the Au4S4 ring motif and Au-PPh3 groups

Cited by 40 publications

References 40 publications

Reactions of GeCl2 with the Thiolate LiSC(SiMe3)3: From thf Activation to Insertion of GeCl2 Molecules into C−S Bonds

Reactions of GeCl2 with the Thiolate LiSC(SiMe3)3: From thf Activation to Insertion of GeCl2 Molecules into C−S Bonds

The Structure–Property Correlations in the Isomerism of Au21(SR)15 Nanoclusters by Density Functional Theory Study

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

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Au₇₀S₂₀(PPh₃)₁₂: an intermediate sized metalloid gold cluster stabilized by the Au₄S₄ ring motif and Au-PPh₃ groups

Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

The Structure–Property Correlations in the Isomerism of Au₂₁(SR)₁₅ Nanoclusters by Density Functional Theory Study