Gas-Phase One-Photon Electronic Spectroscopy of (Arene) chromium Tricarbonyls: Substituent Effects in Multiphoton Dissociation/Ionization Spectra

Dan Rooney; J. Chaiken; D. Driscoll

doi:10.1021/ic00270a023

Gas-Phase One-Photon Electronic Spectroscopy of (Arene) chromium Tricarbonyls: Substituent Effects in Multiphoton Dissociation/Ionization Spectra

Dan Rooney, J. Chaiken, D. Driscoll

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9 Scopus citations

Abstract

We have measured the first gas-phase electronic absorption spectra of (δ⁶-C₆H₆)Cr(CO)₃, (η⁶-C₆H₅Cl)Cr(CO)₃, and (β⁶-C₆H₅CH₃)Cr(CO)₃. Low-resolution, 200-cm^-1, spectra show intense (92000 L/(mol cm)) absorption features extending into the vacuum ultraviolet region indicating the existence of at least five different electronic states with energies below 61 000 cm^-1. Our low-resolution data suggest that only one of those states shifts appreciably with arene substitution. We compare these results with solution-phase spectra and other data. At higher resolution, 40 cm^-1, our data suggest that the onset of detectable absorption is lower in energy for (i;⁶-C₆H₆)Cr(CO)₃than for both (7/⁶-C₆H5Cl)Cr(CO)₃and (η⁶-C₆H₅CH₃)Cr(CO)₃. The fine structure of this transition may be correlated with the well-known photolability of the CO ligands. We discuss these new data in the light of our earlier multiphoton spectroscopy results on these molecules.

Original language	English (US)
Pages (from-to)	3939-3945
Number of pages	7
Journal	Inorganic Chemistry
Volume	26
Issue number	23
DOIs	https://doi.org/10.1021/ic00270a023
State	Published - Nov 1 1987
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Gas-Phase One-Photon Electronic Spectroscopy of (Arene) chromium Tricarbonyls: Substituent Effects in Multiphoton Dissociation/Ionization Spectra",

abstract = "We have measured the first gas-phase electronic absorption spectra of (δ6-C6H6)Cr(CO)3, (η6-C6H5Cl)Cr(CO)3, and (β6-C6H5CH3)Cr(CO)3. Low-resolution, 200-cm-1, spectra show intense (92000 L/(mol cm)) absorption features extending into the vacuum ultraviolet region indicating the existence of at least five different electronic states with energies below 61 000 cm-1. Our low-resolution data suggest that only one of those states shifts appreciably with arene substitution. We compare these results with solution-phase spectra and other data. At higher resolution, 40 cm-1, our data suggest that the onset of detectable absorption is lower in energy for (i;6-C6H6)Cr(CO)3than for both (7/6-C6H5Cl)Cr(CO)3and (η6-C6H5CH3)Cr(CO)3. The fine structure of this transition may be correlated with the well-known photolability of the CO ligands. We discuss these new data in the light of our earlier multiphoton spectroscopy results on these molecules.",

author = "Dan Rooney and J. Chaiken and D. Driscoll",

year = "1987",

month = nov,

day = "1",

doi = "10.1021/ic00270a023",

language = "English (US)",

volume = "26",

pages = "3939--3945",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - Gas-Phase One-Photon Electronic Spectroscopy of (Arene) chromium Tricarbonyls

T2 - Substituent Effects in Multiphoton Dissociation/Ionization Spectra

AU - Rooney, Dan

AU - Chaiken, J.

AU - Driscoll, D.

PY - 1987/11/1

Y1 - 1987/11/1

N2 - We have measured the first gas-phase electronic absorption spectra of (δ6-C6H6)Cr(CO)3, (η6-C6H5Cl)Cr(CO)3, and (β6-C6H5CH3)Cr(CO)3. Low-resolution, 200-cm-1, spectra show intense (92000 L/(mol cm)) absorption features extending into the vacuum ultraviolet region indicating the existence of at least five different electronic states with energies below 61 000 cm-1. Our low-resolution data suggest that only one of those states shifts appreciably with arene substitution. We compare these results with solution-phase spectra and other data. At higher resolution, 40 cm-1, our data suggest that the onset of detectable absorption is lower in energy for (i;6-C6H6)Cr(CO)3than for both (7/6-C6H5Cl)Cr(CO)3and (η6-C6H5CH3)Cr(CO)3. The fine structure of this transition may be correlated with the well-known photolability of the CO ligands. We discuss these new data in the light of our earlier multiphoton spectroscopy results on these molecules.

AB - We have measured the first gas-phase electronic absorption spectra of (δ6-C6H6)Cr(CO)3, (η6-C6H5Cl)Cr(CO)3, and (β6-C6H5CH3)Cr(CO)3. Low-resolution, 200-cm-1, spectra show intense (92000 L/(mol cm)) absorption features extending into the vacuum ultraviolet region indicating the existence of at least five different electronic states with energies below 61 000 cm-1. Our low-resolution data suggest that only one of those states shifts appreciably with arene substitution. We compare these results with solution-phase spectra and other data. At higher resolution, 40 cm-1, our data suggest that the onset of detectable absorption is lower in energy for (i;6-C6H6)Cr(CO)3than for both (7/6-C6H5Cl)Cr(CO)3and (η6-C6H5CH3)Cr(CO)3. The fine structure of this transition may be correlated with the well-known photolability of the CO ligands. We discuss these new data in the light of our earlier multiphoton spectroscopy results on these molecules.

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Gas-Phase One-Photon Electronic Spectroscopy of (Arene) chromium Tricarbonyls: Substituent Effects in Multiphoton Dissociation/Ionization Spectra

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