Unveiling the Nature of Binding Interactions of Acetylene and Ethylene with Triangular Coinage Metal Clusters: A DFT Computational Study
| dc.contributor.author | Tsipis, A. C. | en |
| dc.date.accessioned | 2015-11-24T16:52:01Z | |
| dc.date.available | 2015-11-24T16:52:01Z | |
| dc.identifier.issn | 0276-7333 | - |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/9816 | |
| dc.rights | Default Licence | - |
| dc.subject | effective core potentials | en |
| dc.subject | regular 2-component hamiltonians | en |
| dc.subject | density-functional theory | en |
| dc.subject | diatomic silver cations | en |
| dc.subject | transition-state method | en |
| dc.subject | molecular calculations | en |
| dc.subject | copper(i) ethylene | en |
| dc.subject | ethene complexes | en |
| dc.subject | aromatic-hydrocarbons | en |
| dc.subject | theoretical chemistry | en |
| dc.title | Unveiling the Nature of Binding Interactions of Acetylene and Ethylene with Triangular Coinage Metal Clusters: A DFT Computational Study | en |
| heal.abstract | Density functional theory calculations have been employed to study the molecular and electronic structures, stabilities, and bonding features of a series of metal clusters with the general formulas [c-M(3)L(n)](+) and [c-M(3)(mu(2)-H)(3)L(n)] (M = Cu, Ag, Au, L = ethylene, acetylene; n = 1-3) in their singlet ground states. The upright or in-plane orientation adopted by the eta(2)-coordinated unsaturated hydrocarbon ligands L in the [c-M(3)L(n)](+) and [c-M(3)(mu(2)-H)(3)L(n)] complexes respectively is strongly related to the electrophilicity index, omega, of the respective electrophilic [c-M(3)L(n-1)](+) and [c-M(3)(mu(2)-H)(3)-L(n-1)] fragments. We found that for to omega > 7 eV the unsaturated ligands adopt the upright orientation, while for omega < 2.95 eV the in-plane orientation is adopted. The bending back of the H atoms of acetylene and the pyramidalization of the carbon atoms of ethylene upon coordination of ligands L to the metal centers are due to favorable n(M) -> pi*(L) and pi(L) -> n(M) hyperconjugative interactions. Charge (CDA) and energy decomposition analysis (EDA) indicate that acetylene/ethylene are more strongly bound to the "naked" rather than to the hydrido-bridged triangular noble metal clusters, while the M-C(2)H(2)/C(2)H(4) binding interactions are predicted to be predominantly electrostatic rather than covalent. On the basis of the EDA analysis the contribution of pi-back-bonding, and even delta-back-bonding for the acetylene complexes, to the covalent interactions are far more significant than sigma-bonding in [c-M(3)L(n)](+) clusters, while the opposite holds true for the [c-M(3)(mu(2)-H)(3)L(n)] clusters. | en |
| heal.access | campus | - |
| heal.fullTextAvailability | TRUE | - |
| heal.identifier.primary | Doi 10.1021/Om900781j | - |
| heal.identifier.secondary | <Go to ISI>://000273618600011 | - |
| heal.identifier.secondary | http://pubs.acs.org/doi/abs/10.1021/om900781j | - |
| heal.journalName | Organometallics | en |
| heal.journalType | peer reviewed | - |
| heal.language | en | - |
| heal.publicationDate | 2010 | - |
| heal.recordProvider | Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας | el |
| heal.type | journalArticle | - |
| heal.type.el | Άρθρο Περιοδικού | el |
| heal.type.en | Journal article | en |
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