Dataset Information

Collision-Induced Dissociation of Undecagold Clusters Protected by Mixed Ligands [Au₁₁(PPh₃)₈X₂]⁺ (X = Cl, C?CPh).

ABSTRACT: We herein investigated collision-induced dissociation (CID) processes of undecagold clusters protected by mixed ligands [Au₁₁(PPh₃)₈X₂]⁺ (X = Cl, C?CPh) using mass spectrometry and density functional theory calculations. The results showed that the CID produced fragment ions [Au _x (PPh₃) _y X _z ]⁺ with a formal electron count of eight via sequential loss of PPh₃ ligands and AuX(PPh₃) units in a competitive manner, indicating that the CID channels are governed by the electronic stability of the fragments. Interestingly, the branching fraction of the loss of the AuX(PPh₃) units was significantly smaller for X = C?CPh than that for X = Cl. We ascribed the effect of X on the branching fractions of dissociations of PPh₃ and AuX(PPh₃) to the steric difference.

SUBMITTER: Tomihara R

PROVIDER: S-EPMC6644577 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Collision-Induced Dissociation of Undecagold Clusters Protected by Mixed Ligands [Au11(PPh3)8X2]+ (X = Cl, C≡CPh).

Tomihara Ryohei R Hirata Keisuke K Yamamoto Hiroki H Takano Shinjiro S Koyasu Kiichirou K Tsukuda Tatsuya T

ACS omega 20180611 6

We herein investigated collision-induced dissociation (CID) processes of undecagold clusters protected by mixed ligands [Au11(PPh3)8X2]+ (X = Cl, C≡CPh) using mass spectrometry and density functional theory calculations. The results showed that the CID produced fragment ions [Au x (PPh3) y X z ]+ with a formal electron count of eight via sequential loss of PPh3< ...[more]

PMID: 31458806

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Project description: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(?3-S)8, Ag6@Au12(?3-S)8 and Au6@Au12(?3-S)8, which exhibit high thermostability and may be synthesized in future.

Dataset Information

Collision-Induced Dissociation of Undecagold Clusters Protected by Mixed Ligands [Au₁₁(PPh₃)₈X₂]⁺ (X = Cl, C?CPh).

Publications

Collision-Induced Dissociation of Undecagold Clusters Protected by Mixed Ligands [Au<sub>11</sub>(PPh<sub>3</sub>)<sub>8</sub>X<sub>2</sub>]<sup>+</sup> (X = Cl, C≡CPh).

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OmicsDI is part of the ELIXIR infrastructure

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Dataset Information

Collision-Induced Dissociation of Undecagold Clusters Protected by Mixed Ligands [Au11(PPh3)8X2]+ (X = Cl, C?CPh).

Publications

Collision-Induced Dissociation of Undecagold Clusters Protected by Mixed Ligands [Au<sub>11</sub>(PPh<sub>3</sub>)<sub>8</sub>X<sub>2</sub>]<sup>+</sup> (X = Cl, C≡CPh).

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Collision-Induced Dissociation of Undecagold Clusters Protected by Mixed Ligands [Au₁₁(PPh₃)₈X₂]⁺ (X = Cl, C?CPh).