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Structural and bonding trends in platinum-carbon clusters

Miller, Thomas F., III and Hall, Michael B. (1999) Structural and bonding trends in platinum-carbon clusters. Journal of the American Chemical Society, 121 (32). pp. 7389-7396. ISSN 0002-7863. doi:10.1021/ja990854n.

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Density functional calculations with the B3-LYP functional were used to optimize the platinum−carbon cationic clusters, PtC_x^+, 1 ≤ x ≤ 16, in both the doublet and quartet states of the linear, fan, open-ring, closed-ring, and one-carbon-ring geometries. Trends in stability, Pt^+−C_x binding energy, doublet-quartet excitation energy, and Pt−C bond lengths were investigated. Explanations for these patterns are provided in terms of orbital interactions and changes imposed on the carbon chain by the metal atom. In accord with the previously studied palladium−carbon cations, the PtC_x^+ clusters favored a linear geometry for 3 ≤ x ≤ 9. For larger clusters, the open-ring (Pt inserted in C_x ring) and closed-ring (Pt bound to two atoms of closed C_x ring) families exhibit the lowest-energy structures. The stability and the nature of the Pt−C bonding in both the closed-ring and one-carbon-ring (Pt bound to one atom of closed C_x ring) PtC_x^+ structures depend greatly on the aromaticity of the corresponding C_x ring. However, unlike their palladium counterparts, the closed-ring platinum clusters were found invariably to be more stable than the respective one-carbon species. The stability of forming two Pt−C σ bonds is due to relatively lower energy sd hybrid orbitals from the platinum cation.

Item Type:Article
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URLURL TypeDescription DOIArticle
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 1999 American Chemical Society. Received March 17, 1999. Revised Manuscript Received June 9, 1999. Published on Web 08/03/1999. We thank the National Science Foundation (Grant Nos. CHE 94-23271, CHE 98-00184, and CHE 95-28196) and the Robert A. Welch Foundation (Grant No. A-648) for financial support.
Funding AgencyGrant Number
NSFCHE 94-23271
NSFCHE 98-00184
NSFCHE 95-28196
Robert A. Welch FoundationA-648
Issue or Number:32
Record Number:CaltechAUTHORS:20130301-152550052
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Official Citation:Structural and Bonding Trends in Platinum−Carbon Clusters Thomas F. Miller III and and Michael B. Hall Journal of the American Chemical Society1999121 (32), 7389-7396
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:37257
Deposited By: Tony Diaz
Deposited On:04 Mar 2013 23:59
Last Modified:09 Nov 2021 23:27

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