Wavelength Dependence of Excimer Laser Photolysis of Cr(CO)6 in the Gas Phase. A Study of the Infrared Spectroscopy and Reactions of the Cr(CO)x (x = 5, 4, 3, 2) Fragments

T. A. Seder; Stephen P. Church; Eric Weitz

doi:10.1021/ja00276a007

Wavelength Dependence of Excimer Laser Photolysis of Cr(CO)₆ in the Gas Phase. A Study of the Infrared Spectroscopy and Reactions of the Cr(CO)_x (x = 5, 4, 3, 2) Fragments

T. A. Seder, Stephen P. Church, Eric Weitz^*

^*Corresponding author for this work

Chemistry

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Abstract

The transient infrared absorption spectra of the coordinatively unsaturated Cr(CO)_x species (x = 5, 4, 3, and 2) that are generated via excimer laser photolysis of gas-phase Cr(CO)₆ are presented and discussed. The photofragments produced upon 193-, 248-, and 351-nm photolysis are identified. The results indicate that the gas-phase structures of the Cr(CO)_x species are the same as those observed in condensed-phase experiments. It is postulated that Cr(CO)₅ adopts a Cu, structure, Cr(CO)₄ adopts a C_2υ structure, and Cr(CO)₃ adopts a C_3υ, structure. The coordinatively unsaturated species are, in general, observed to be produced with a significant amount of internal excitation. The rate constants for the reaction of Cr(CO)₅, Cr(CO)₄, and Cr(CO)₃ with CO were measured and found to be 1.5 × 10¹³, 2.4 × 10¹³, and 1.8 × 10¹³ cm³ mol^–1 s^–1, respectively.

Original language	English (US)
Pages (from-to)	4721-4728
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	108
Issue number	16
DOIs	https://doi.org/10.1021/ja00276a007
State	Published - 1986

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Wavelength Dependence of Excimer Laser Photolysis of Cr(CO)6 in the Gas Phase. A Study of the Infrared Spectroscopy and Reactions of the Cr(CO)x (x = 5, 4, 3, 2) Fragments",

abstract = "The transient infrared absorption spectra of the coordinatively unsaturated Cr(CO)x species (x = 5, 4, 3, and 2) that are generated via excimer laser photolysis of gas-phase Cr(CO)6 are presented and discussed. The photofragments produced upon 193-, 248-, and 351-nm photolysis are identified. The results indicate that the gas-phase structures of the Cr(CO)x species are the same as those observed in condensed-phase experiments. It is postulated that Cr(CO)5 adopts a Cu, structure, Cr(CO)4 adopts a C2υ structure, and Cr(CO)3 adopts a C3υ, structure. The coordinatively unsaturated species are, in general, observed to be produced with a significant amount of internal excitation. The rate constants for the reaction of Cr(CO)5, Cr(CO)4, and Cr(CO)3 with CO were measured and found to be 1.5 × 1013, 2.4 × 1013, and 1.8 × 1013 cm3 mol–1 s–1, respectively.",

author = "Seder, {T. A.} and Church, {Stephen P.} and Eric Weitz",

year = "1986",

doi = "10.1021/ja00276a007",

language = "English (US)",

volume = "108",

pages = "4721--4728",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "16",

}

Wavelength Dependence of Excimer Laser Photolysis of Cr(CO)₆ in the Gas Phase. A Study of the Infrared Spectroscopy and Reactions of the Cr(CO)_x (x = 5, 4, 3, 2) Fragments. / Seder, T. A.; Church, Stephen P.; Weitz, Eric.
In: Journal of the American Chemical Society, Vol. 108, No. 16, 1986, p. 4721-4728.

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

TY - JOUR

T1 - Wavelength Dependence of Excimer Laser Photolysis of Cr(CO)6 in the Gas Phase. A Study of the Infrared Spectroscopy and Reactions of the Cr(CO)x (x = 5, 4, 3, 2) Fragments

AU - Seder, T. A.

AU - Church, Stephen P.

AU - Weitz, Eric

PY - 1986

Y1 - 1986

N2 - The transient infrared absorption spectra of the coordinatively unsaturated Cr(CO)x species (x = 5, 4, 3, and 2) that are generated via excimer laser photolysis of gas-phase Cr(CO)6 are presented and discussed. The photofragments produced upon 193-, 248-, and 351-nm photolysis are identified. The results indicate that the gas-phase structures of the Cr(CO)x species are the same as those observed in condensed-phase experiments. It is postulated that Cr(CO)5 adopts a Cu, structure, Cr(CO)4 adopts a C2υ structure, and Cr(CO)3 adopts a C3υ, structure. The coordinatively unsaturated species are, in general, observed to be produced with a significant amount of internal excitation. The rate constants for the reaction of Cr(CO)5, Cr(CO)4, and Cr(CO)3 with CO were measured and found to be 1.5 × 1013, 2.4 × 1013, and 1.8 × 1013 cm3 mol–1 s–1, respectively.

AB - The transient infrared absorption spectra of the coordinatively unsaturated Cr(CO)x species (x = 5, 4, 3, and 2) that are generated via excimer laser photolysis of gas-phase Cr(CO)6 are presented and discussed. The photofragments produced upon 193-, 248-, and 351-nm photolysis are identified. The results indicate that the gas-phase structures of the Cr(CO)x species are the same as those observed in condensed-phase experiments. It is postulated that Cr(CO)5 adopts a Cu, structure, Cr(CO)4 adopts a C2υ structure, and Cr(CO)3 adopts a C3υ, structure. The coordinatively unsaturated species are, in general, observed to be produced with a significant amount of internal excitation. The rate constants for the reaction of Cr(CO)5, Cr(CO)4, and Cr(CO)3 with CO were measured and found to be 1.5 × 1013, 2.4 × 1013, and 1.8 × 1013 cm3 mol–1 s–1, respectively.

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Wavelength Dependence of Excimer Laser Photolysis of Cr(CO)₆ in the Gas Phase. A Study of the Infrared Spectroscopy and Reactions of the Cr(CO)_x (x = 5, 4, 3, 2) Fragments

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