Laser Pulse Photolysis and Transient Infrared Investigation into the Effect of Solvent or Substituents (X) on the Reactivity of Photogenerated (η6-C6H6-yXy)Cr(CO)2 Intermediates

Bernadette S. Creaven; Michael W. George; Allan G. Ginzburg; Catherine Hughes; John M. Kelly; Conor Long; Irene M. McGrath; Mary T. Pryce

doi:10.1021/om00032a040

Laser Pulse Photolysis and Transient Infrared Investigation into the Effect of Solvent or Substituents (X) on the Reactivity of Photogenerated (η⁶-C₆H₆-_yX_y)Cr(CO)₂ Intermediates

Bernadette S. Creaven, Michael W. George, Allan G. Ginzburg, Catherine Hughes, John M. Kelly, Conor Long, Irene M. McGrath, Mary T. Pryce

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

59 Citations (Scopus)

Abstract

Time-resolved infrared spectroscopy identified the first observable species following nanosecond laser photolysis of (benzene)Cr(CO)₃ in alkane solution as (benzene)Cr(CO)₂(alkane). UV/vis-monitored laser flash photolysis was used to observe the reaction of this species with CO. The reactivity toward CO of the primary photoproducts derived from related arene complexes (arene = C₆H₅Cl, C₅H₅Me, p-ClC₆H₄Me, C₆H₅Et, C₆H₅Bu^t, o- and p-C₆H₄Me₂, C₆H₃Me₃, C₆Me₆, C₆Et₆) were also determined by this technique. The rate of reaction with CO was found to depend on the alkane solvent and on the nature and degree of substitution of the arene ligand. The enthalpies of activation for all reactions were constant (24 ± 2 kJ mol⁻¹), while the entropy of activation increased upon methyl substitution of the arene and upon a change in the solvent from cyclohexane to a linear alkane.

Original language	English
Pages (from-to)	3127-3131
Number of pages	5
Journal	Organometallics
Volume	12
Issue number	8
DOIs	https://doi.org/10.1021/om00032a040
Publication status	Published - 1993

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Creaven, B. S., George, M. W., Ginzburg, A. G., Hughes, C., Kelly, J. M., Long, C., McGrath, I. M., & Pryce, M. T. (1993). Laser Pulse Photolysis and Transient Infrared Investigation into the Effect of Solvent or Substituents (X) on the Reactivity of Photogenerated (η⁶-C₆H₆-_yX_y)Cr(CO)₂ Intermediates. Organometallics, 12(8), 3127-3131. https://doi.org/10.1021/om00032a040

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title = "Laser Pulse Photolysis and Transient Infrared Investigation into the Effect of Solvent or Substituents (X) on the Reactivity of Photogenerated (η6-C6H6-yXy)Cr(CO)2 Intermediates",

abstract = "Time-resolved infrared spectroscopy identified the first observable species following nanosecond laser photolysis of (benzene)Cr(CO)3 in alkane solution as (benzene)Cr(CO)2(alkane). UV/vis-monitored laser flash photolysis was used to observe the reaction of this species with CO. The reactivity toward CO of the primary photoproducts derived from related arene complexes (arene = C6H5Cl, C5H5Me, p-ClC6H4Me, C6H5Et, C6H5But, o- and p-C6H4Me2, C6H3Me3, C6Me6, C6Et6) were also determined by this technique. The rate of reaction with CO was found to depend on the alkane solvent and on the nature and degree of substitution of the arene ligand. The enthalpies of activation for all reactions were constant (24 ± 2 kJ mol−1), while the entropy of activation increased upon methyl substitution of the arene and upon a change in the solvent from cyclohexane to a linear alkane.",

author = "Creaven, {Bernadette S.} and George, {Michael W.} and Ginzburg, {Allan G.} and Catherine Hughes and Kelly, {John M.} and Conor Long and McGrath, {Irene M.} and Pryce, {Mary T.}",

year = "1993",

doi = "10.1021/om00032a040",

language = "English",

volume = "12",

pages = "3127--3131",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "8",

}

Laser Pulse Photolysis and Transient Infrared Investigation into the Effect of Solvent or Substituents (X) on the Reactivity of Photogenerated (η⁶-C₆H₆-_yX_y)Cr(CO)₂ Intermediates. / Creaven, Bernadette S.; George, Michael W.; Ginzburg, Allan G. et al.
In: Organometallics, Vol. 12, No. 8, 1993, p. 3127-3131.

Research output: Journal Publication › Article › peer-review

TY - JOUR

T1 - Laser Pulse Photolysis and Transient Infrared Investigation into the Effect of Solvent or Substituents (X) on the Reactivity of Photogenerated (η6-C6H6-yXy)Cr(CO)2 Intermediates

AU - Creaven, Bernadette S.

AU - George, Michael W.

AU - Ginzburg, Allan G.

AU - Hughes, Catherine

AU - Kelly, John M.

AU - Long, Conor

AU - McGrath, Irene M.

AU - Pryce, Mary T.

PY - 1993

Y1 - 1993

N2 - Time-resolved infrared spectroscopy identified the first observable species following nanosecond laser photolysis of (benzene)Cr(CO)3 in alkane solution as (benzene)Cr(CO)2(alkane). UV/vis-monitored laser flash photolysis was used to observe the reaction of this species with CO. The reactivity toward CO of the primary photoproducts derived from related arene complexes (arene = C6H5Cl, C5H5Me, p-ClC6H4Me, C6H5Et, C6H5But, o- and p-C6H4Me2, C6H3Me3, C6Me6, C6Et6) were also determined by this technique. The rate of reaction with CO was found to depend on the alkane solvent and on the nature and degree of substitution of the arene ligand. The enthalpies of activation for all reactions were constant (24 ± 2 kJ mol−1), while the entropy of activation increased upon methyl substitution of the arene and upon a change in the solvent from cyclohexane to a linear alkane.

AB - Time-resolved infrared spectroscopy identified the first observable species following nanosecond laser photolysis of (benzene)Cr(CO)3 in alkane solution as (benzene)Cr(CO)2(alkane). UV/vis-monitored laser flash photolysis was used to observe the reaction of this species with CO. The reactivity toward CO of the primary photoproducts derived from related arene complexes (arene = C6H5Cl, C5H5Me, p-ClC6H4Me, C6H5Et, C6H5But, o- and p-C6H4Me2, C6H3Me3, C6Me6, C6Et6) were also determined by this technique. The rate of reaction with CO was found to depend on the alkane solvent and on the nature and degree of substitution of the arene ligand. The enthalpies of activation for all reactions were constant (24 ± 2 kJ mol−1), while the entropy of activation increased upon methyl substitution of the arene and upon a change in the solvent from cyclohexane to a linear alkane.

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DO - 10.1021/om00032a040

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SN - 0276-7333

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JO - Organometallics

JF - Organometallics

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Laser Pulse Photolysis and Transient Infrared Investigation into the Effect of Solvent or Substituents (X) on the Reactivity of Photogenerated (η⁶-C₆H₆-_yX_y)Cr(CO)₂ Intermediates

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