Synthesis and gas-phase uni- and bi-molecular reactivity of bisphosphine ligated gold clusters, [AuxLy]n+

Robinson, Peter S. D.; Nguyen, Tich-Lam; Lioe, Hadi; O’Hair, Richard A. J.; Khairallah, George N.

doi:10.1016/j.ijms.2012.07.005

Cited by 30 publications

(35 citation statements)

References 76 publications

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“…These dissociation products are listed in Table S2. The CID of Au 10 L 4 2 + clusters ligated with related phenyl-substituted diphosphine ligands containing five [16] as well as three to six [24] carbon atoms in the alkyl chain have been reported previously. In the case of the dppp ligand with a three-carbonatom chain, which is most similar to the dcpp ligand in our current study, Au 10 L 4 2 + (L = dppp) was shown to fragment by loss of a neutral ligand.…”

Section: Resultssupporting

confidence: 55%

“…[16] The results of Bergeron and co-workers agree qualitatively with the more recent study by Robinson and co-workers, which found loss of a neutral ligand from Au 11 L 5 3 + (L = dppp) forming Au 11 L 4 3 + to be an additional minor fragmentation channel. [24] Therefore, triply charged cationic gold clusters ligated with dcpp and dppp share some similar fragmentation pathways that produce small singly charged AuL + and Au 3 L + ions along with the larger doubly charged complementary ions. In comparison with Au 11 L 5 3 + (L = dppp), the smaller Au 9 L 4 3 + (L = dcpp) does not show any loss of a neutral ligand from the precursor ion.…”

Section: Resultsmentioning

confidence: 99%

“…[16][17][18][19][20][21][22][23][24] Specifically, experiments by Bergeron and co-workers demonstrated singly charged AuL + (L = dppp) to be the dominant CID fragment along with the complementary doubly charged Au 10 L 4 2 + ion. A second, less abundant set of complementary fragment ions, Au 3 L + and Au 8 L 4 2 + , was also observed.…”

Section: Resultsmentioning

confidence: 99%

“…However, the fragmentation of a closely related Au 6 L 3 2 + cluster ligated with 1,4-bis(diphenylphosphino)butane (dppb), which contains four instead of three carbon atoms in the alkyl chain separating the two phosphine groups, has been investigated. [24] The dppb-capped cluster undergoes fragmentation Figure 3a.…”

Section: Resultsmentioning

confidence: 99%

“…Analogous losses of Au(C 6 H 5 ) from cationic gold clusters capped with several different-length phenyl-substituted diphosphine ligands were reported previously by Robinson and co-workers. [24] There is also a precedent for the formation of closely related Au(C 6 H 6 )…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Characterization of Gold Clusters Ligated with 1,3‐Bis(dicyclohexylphosphino)propane

2013

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In this multidisciplinary study the chemical reduction synthesis of novel gold clusters in solution was combined with high‐resolution analytical mass spectrometry (MS) to gain insight into the composition of the gold clusters and how their size, ionic charge state, and ligand substitution influences their gas‐phase fragmentation pathways. Ultrasmall cationic gold clusters ligated with 1,3‐bis(dicyclohexylphosphino)propane (dcpp) were synthesized for the first time and introduced into the gas phase using electrospray ionization (ESI). Mass‐selected cluster ions were fragmented by employing collision‐induced dissociation (CID) and the product ions were analyzed using MS. The solutions were found to contain the multiply charged cationic gold clusters Au9L43+, Au13L53+, Au6L32+, Au8L32+, and Au10L42+ (L=dcpp). The gas‐phase fragmentation pathways of these cluster ions were examined systematically by employing CID combined with MS. In addition, CID experiments were performed on related gold clusters of the same size and ionic charge state but capped with 1,3‐bis(diphenylphosphino)propane (dppp) ligands containing phenyl functional groups at the two phosphine centers instead of cyclohexane rings. It is shown that this relatively small change in the molecular substitution of the two phosphine centers in diphosphine ligands (C6H11 versus C6H5) exerts a pronounced influence on the size of the species that are preferentially formed in solution during reduction synthesis as well as the gas‐phase fragmentation channels of otherwise identical gold cluster ions. The mass spectrometry results indicate that in addition to the length of the alkyl chain between the two phosphine centers, the substituents at the phosphine centers also play a crucial role in determining the composition, size, and stability of diphosphine‐ligated gold clusters synthesized in solution.

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Section: Resultssupporting

confidence: 55%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthesis and Characterization of Gold Clusters Ligated with 1,3‐Bis(dicyclohexylphosphino)propane

2013

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A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

et al. 2022

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Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties of ligated gold clusters are strongly defined by the metal-ligand interaction and type of ligands. This critical feature renders gold-phosphine clusters unique and distinct from other ligand-protected gold clusters. The use of multidentate phosphines enables preparation of varying core sizes and exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange and removal for specific applications, such as catalysis, without agglomeration. The aim of this review is to provide a unified view of gold-phosphine clusters and to present an in-depth discussion on recent advances and key developments for these clusters. This review features the unique chemistry, structural, electronic, and optical properties of gold-phosphine clusters. Advanced characterization techniques, including synchrotron-based spectroscopy, have unraveled substantial effects of Au-P interaction on the composition-, structure-, and size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings are also discussed. Finally, a discussion of the application of gold-phosphine clusters in catalysis is presented.

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On‐Line Reaction Monitoring and Mechanistic Studies by Mass Spectrometry: Negishi Cross‐Coupling, Hydrogenolysis, and Reductive Amination

Yan

Sokol

et al. 2014

Angewandte Chemie

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Reaction monitoring using inductive ESI mass spectrometry allows chemical reactions to be tracked in real time, including air‐ and moisture‐sensitive as well as heterogeneous reactions. Highly concentrated solutions can also be monitored for long periods without emitter clogging. Sheath gas assists in nebulization and a sample splitter reduces the delay time and minimizes contamination of the instrument. Short‐lived intermediates (ca. 5 s) were observed in Pd/C‐catalyzed hydrogenolysis, and several intermediates were seen in Negishi cross‐coupling reactions.

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Synthesis and gas-phase uni- and bi-molecular reactivity of bisphosphine ligated gold clusters, [AuxLy]n+

Cited by 30 publications

References 76 publications

Synthesis and Characterization of Gold Clusters Ligated with 1,3‐Bis(dicyclohexylphosphino)propane

Synthesis and Characterization of Gold Clusters Ligated with 1,3‐Bis(dicyclohexylphosphino)propane

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

On‐Line Reaction Monitoring and Mechanistic Studies by Mass Spectrometry: Negishi Cross‐Coupling, Hydrogenolysis, and Reductive Amination

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