The electronic structure of transition metal carbonyl complexes

Baerends, Evert Jan; Ros, P.

doi:10.1080/00268977500103261

Cited by 159 publications

(27 citation statements)

References 41 publications

(73 reference statements)

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“…A linear relationship between the calculated CO(2π) orbital occupation P(2π) and experimental ν(CO) frequencies, in terms of the stretching force constants F CO , has been established in earlier studies [75,76] …”

Section: Effects Of Electron Densitymentioning

confidence: 99%

The adsorption of CO on transition metal clusters: A case study of cluster surface chemistry

et al. 2009

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We present a discussion of recent experimental studies on the interaction of single CO molecules with transition metal clusters in the gas phase, typically in the size-range of 3 to more than 20 atoms, emphasizing specifically the insights gained from vibrational spectroscopy. Trends across the transition metals for molecular vs. dissociative chemisorption as well as for adsorption geometries are discussed and compared with the behaviour of CO adsorbed on extended surfaces. The dependence of the frequency of the internal CO stretch vibration on the size and charge of the cluster enables one to gauge quantitatively the effects of charge transfer between deposited nano-particles and the substrate as well as of electron transfer due to the binding of co-adsorbed species.

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Section: Effects Of Electron Densitymentioning

confidence: 99%

The adsorption of CO on transition metal clusters: A case study of cluster surface chemistry

et al. 2009

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“…22,23 A quantitative framework for evaluating ͑CO͒ follows from early studies that established a linear relationship between calculated CO 2 * orbital populations and experimental frequencies in metal carbonyl compounds. 24,25 Under the assumption that the effect of bonding is not significant, as discussed above, extension of this approach to include the change induced by the electrostatic effect, ⌬F ES , gives the C-O stretching force constant F CO as follows:…”

Section: -mentioning

confidence: 99%

Size and charge effects on the binding of CO to late transition metal clusters

Fielicke

Helden

Meijer

et al. 2006

The Journal of Chemical Physics

111

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We report on the size and charge dependence of the C-O stretching frequency, ͑CO͒, in complexes of CO with gas phase anionic, neutral, and cationic cobalt clusters ͑Co n CO −/0/+ ͒, anionic, neutral, and cationic rhodium clusters ͑Rh n CO −/0/+ ͒, and cationic nickel clusters ͑Ni n CO + ͒ for n up to 37. We develop models, based on the established vibrational spectroscopy of organometallic carbonyl compounds, to understand how cluster size and charge relate to ͑CO͒ in these complexes. The dominating factor is the available electron density for backdonation from the metal to the CO * orbital. Electrostatic effects play a significant but minor role. For the charged clusters, the size trends are related to the dilution of the charge density at the binding site on the cluster as n increases. At large n, ͑CO͒ approaches asymptotes that are not the same as found for ͑CO͒ on the single crystal metal surfaces, reflecting differences between binding sites on medium sized clusters and the more highly coordinated metal surface sites.

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“…always a competing channel for energy disposal that we cannot monitor. From molecular orbital analyses for iron and nickel carbonyl ( Baerends and Ros, 1975), the metal atoms possess a formal positive charge in the molecular state, so the electron from the rare gas atom would land in an empty metal orbital. The orbital would be antibonding toward metal-ligand bonding and would lead to an instantaneous repulsive interaction leading in turn to a simultaneous dissolution of the metal-CO bonds.…”

Section: Discussionmentioning

confidence: 99%

Metal-atom fluorescence from the quenching of metastable rare gases by metal carbonyls

Hollingsworth¹

1982

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The electronic structure of transition metal carbonyl complexes

Cited by 159 publications

References 41 publications

The adsorption of CO on transition metal clusters: A case study of cluster surface chemistry

The adsorption of CO on transition metal clusters: A case study of cluster surface chemistry

Size and charge effects on the binding of CO to late transition metal clusters

Metal-atom fluorescence from the quenching of metastable rare gases by metal carbonyls

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