Gas-Phase Helium I Photoelectron Spectra of Methinyltricobalt Enneacarbonyl Clusters

Gaetano Granozzi; Eugenio Tondello; David Ajò; Maurizio Casarin; Silvio Aime; Domenico Osella

doi:10.1021/ic00133a041

Gas-Phase Helium I Photoelectron Spectra of Methinyltricobalt Enneacarbonyl Clusters

Gaetano Granozzi, Eugenio Tondello, David Ajò, Maurizio Casarin, Silvio Aime, Domenico Osella

Research output: Contribution to journal › Article › peer-review

Abstract

The electronic structure of Co₃(CO)₉CY clusters, where Y = H, F, Cl, Br, I, CH₃, CF₃, or COOCH₃, is discussed on the basis of their He I excited gas-phase photoelectron spectra. A qualitative energy level diagram has been afforded which allows a satisfactory discussion of the PE data. The most interesting feature of our interpretative model is the presence of a molecular orbital of e symmetry which accounts for a large portion of the interaction between the Co₃ triangle and the apical carbon atom C_ap and for the electron transmission from the apical substituent Y and the cobalt atoms via a resonance-type mechanism. In agreement with previous NQR and IR data, evidence for significant Y→C_ap π-bonding donation with Y = Cl, Br, or I is presented. The relationships existing between the present clusters and molecules of type M₃(CO)₁₂ and (µ-CH₂)[ML_n]₂ have been stressed.

Original language	English
Pages (from-to)	1081-1084
Number of pages	4
Journal	Inorganic Chemistry
Volume	21
Issue number	3
DOIs	https://doi.org/10.1021/ic00133a041
Publication status	Published - 1982
Externally published	Yes

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title = "Gas-Phase Helium I Photoelectron Spectra of Methinyltricobalt Enneacarbonyl Clusters",

abstract = "The electronic structure of Co3(CO)9CY clusters, where Y = H, F, Cl, Br, I, CH3, CF3, or COOCH3, is discussed on the basis of their He I excited gas-phase photoelectron spectra. A qualitative energy level diagram has been afforded which allows a satisfactory discussion of the PE data. The most interesting feature of our interpretative model is the presence of a molecular orbital of e symmetry which accounts for a large portion of the interaction between the Co3 triangle and the apical carbon atom Cap and for the electron transmission from the apical substituent Y and the cobalt atoms via a resonance-type mechanism. In agreement with previous NQR and IR data, evidence for significant Y→Cap π-bonding donation with Y = Cl, Br, or I is presented. The relationships existing between the present clusters and molecules of type M3(CO)12 and (µ-CH2)[MLn]2 have been stressed.",

author = "Gaetano Granozzi and Eugenio Tondello and David Aj{\`o} and Maurizio Casarin and Silvio Aime and Domenico Osella",

year = "1982",

doi = "10.1021/ic00133a041",

language = "English",

volume = "21",

pages = "1081--1084",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Gas-Phase Helium I Photoelectron Spectra of Methinyltricobalt Enneacarbonyl Clusters

AU - Granozzi, Gaetano

AU - Tondello, Eugenio

AU - Ajò, David

AU - Casarin, Maurizio

AU - Aime, Silvio

AU - Osella, Domenico

PY - 1982

Y1 - 1982

N2 - The electronic structure of Co3(CO)9CY clusters, where Y = H, F, Cl, Br, I, CH3, CF3, or COOCH3, is discussed on the basis of their He I excited gas-phase photoelectron spectra. A qualitative energy level diagram has been afforded which allows a satisfactory discussion of the PE data. The most interesting feature of our interpretative model is the presence of a molecular orbital of e symmetry which accounts for a large portion of the interaction between the Co3 triangle and the apical carbon atom Cap and for the electron transmission from the apical substituent Y and the cobalt atoms via a resonance-type mechanism. In agreement with previous NQR and IR data, evidence for significant Y→Cap π-bonding donation with Y = Cl, Br, or I is presented. The relationships existing between the present clusters and molecules of type M3(CO)12 and (µ-CH2)[MLn]2 have been stressed.

AB - The electronic structure of Co3(CO)9CY clusters, where Y = H, F, Cl, Br, I, CH3, CF3, or COOCH3, is discussed on the basis of their He I excited gas-phase photoelectron spectra. A qualitative energy level diagram has been afforded which allows a satisfactory discussion of the PE data. The most interesting feature of our interpretative model is the presence of a molecular orbital of e symmetry which accounts for a large portion of the interaction between the Co3 triangle and the apical carbon atom Cap and for the electron transmission from the apical substituent Y and the cobalt atoms via a resonance-type mechanism. In agreement with previous NQR and IR data, evidence for significant Y→Cap π-bonding donation with Y = Cl, Br, or I is presented. The relationships existing between the present clusters and molecules of type M3(CO)12 and (µ-CH2)[MLn]2 have been stressed.

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DO - 10.1021/ic00133a041

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

Gas-Phase Helium I Photoelectron Spectra of Methinyltricobalt Enneacarbonyl Clusters

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