Photodissociation Pathways and Recombination Kinetics for Gas-Phase Mn2(CO)10

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

doi:10.1021/ja00284a013

Photodissociation Pathways and Recombination Kinetics for Gas-Phase Mn₂(CO)₁₀

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

^*Corresponding author for this work

Chemistry

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

68 Scopus citations

Abstract

Both Mn(CO)₅ and Mn₂(CO)₉ are observed following gas-phase photolysis of Mn₂(CO)₁₀. The Mn(CO)₅/Mn₂(CO)₉ ratio can be shifted to favor formation of Mn₂(CO)₉ by increasing the photolysis energy from 351 to 248 to 193 nm. Mn(CO)₅ is formed with significant amounts of internal excitation. Further, as the photolysis energy increases, additional photoproducts are produced which are tentatively assigned as predominantly Mn₂(CO)_x species (x < 9). IR absorptions of both Mn(CO)₅ and Mn₂(CO)₉ have been recorded and assigned in the range ~2050 to ~ 1750 cm^-1. The rate constant for the reaction of two Mn(CO)₅ radicals to form Mn₂(CO)_l0 has been measured and found to be near gas kinetic. The rate constant for the reaction of Mn₂(CO)₉ with CO to form Mn₂(CO)_l0 has been determined to be (2.4 ± 0.8) × 10⁶ L mol^-1 s^-1.

Original language	English (US)
Pages (from-to)	7518-7524
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	108
Issue number	24
DOIs	https://doi.org/10.1021/ja00284a013
State	Published - 1986

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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@article{c3d0d8cec6b94dbba2a3d28f154a8eab,

title = "Photodissociation Pathways and Recombination Kinetics for Gas-Phase Mn2(CO)10",

abstract = "Both Mn(CO)5 and Mn2(CO)9 are observed following gas-phase photolysis of Mn2(CO)10. The Mn(CO)5/Mn2(CO)9 ratio can be shifted to favor formation of Mn2(CO)9 by increasing the photolysis energy from 351 to 248 to 193 nm. Mn(CO)5 is formed with significant amounts of internal excitation. Further, as the photolysis energy increases, additional photoproducts are produced which are tentatively assigned as predominantly Mn2(CO)x species (x < 9). IR absorptions of both Mn(CO)5 and Mn2(CO)9 have been recorded and assigned in the range ~2050 to ~ 1750 cm-1. The rate constant for the reaction of two Mn(CO)5 radicals to form Mn2(CO)l0 has been measured and found to be near gas kinetic. The rate constant for the reaction of Mn2(CO)9 with CO to form Mn2(CO)l0 has been determined to be (2.4 ± 0.8) × 106 L mol-1 s-1.",

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

year = "1986",

doi = "10.1021/ja00284a013",

language = "English (US)",

volume = "108",

pages = "7518--7524",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "24",

}

TY - JOUR

T1 - Photodissociation Pathways and Recombination Kinetics for Gas-Phase Mn2(CO)10

AU - Seder, T. A.

AU - Church, Stephen P.

AU - Weitz, Eric

PY - 1986

Y1 - 1986

N2 - Both Mn(CO)5 and Mn2(CO)9 are observed following gas-phase photolysis of Mn2(CO)10. The Mn(CO)5/Mn2(CO)9 ratio can be shifted to favor formation of Mn2(CO)9 by increasing the photolysis energy from 351 to 248 to 193 nm. Mn(CO)5 is formed with significant amounts of internal excitation. Further, as the photolysis energy increases, additional photoproducts are produced which are tentatively assigned as predominantly Mn2(CO)x species (x < 9). IR absorptions of both Mn(CO)5 and Mn2(CO)9 have been recorded and assigned in the range ~2050 to ~ 1750 cm-1. The rate constant for the reaction of two Mn(CO)5 radicals to form Mn2(CO)l0 has been measured and found to be near gas kinetic. The rate constant for the reaction of Mn2(CO)9 with CO to form Mn2(CO)l0 has been determined to be (2.4 ± 0.8) × 106 L mol-1 s-1.

AB - Both Mn(CO)5 and Mn2(CO)9 are observed following gas-phase photolysis of Mn2(CO)10. The Mn(CO)5/Mn2(CO)9 ratio can be shifted to favor formation of Mn2(CO)9 by increasing the photolysis energy from 351 to 248 to 193 nm. Mn(CO)5 is formed with significant amounts of internal excitation. Further, as the photolysis energy increases, additional photoproducts are produced which are tentatively assigned as predominantly Mn2(CO)x species (x < 9). IR absorptions of both Mn(CO)5 and Mn2(CO)9 have been recorded and assigned in the range ~2050 to ~ 1750 cm-1. The rate constant for the reaction of two Mn(CO)5 radicals to form Mn2(CO)l0 has been measured and found to be near gas kinetic. The rate constant for the reaction of Mn2(CO)9 with CO to form Mn2(CO)l0 has been determined to be (2.4 ± 0.8) × 106 L mol-1 s-1.

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DO - 10.1021/ja00284a013

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 24

ER -

Photodissociation Pathways and Recombination Kinetics for Gas-Phase Mn₂(CO)₁₀

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