Photochemistry of [CpMo(CO)3]2. Direct Detection and Kinetics of the Radical CpMo(CO)3 in n-Heptane Solution at Room Temperature by Fast Time-Resolved Infrared Spectroscopy

Jonas Peters; Michael W. George; James J. Turner

doi:10.1021/om00003a060

Photochemistry of [CpMo(CO)₃]₂. Direct Detection and Kinetics of the Radical CpMo(CO)₃ in n-Heptane Solution at Room Temperature by Fast Time-Resolved Infrared Spectroscopy

Jonas Peters, Michael W. George, James J. Turner

Research output: Journal Publication › Article › peer-review

44 Citations (Scopus)

Abstract

Fast (nanosecond) time-resolved infrared spectroscopy has been used to follow the visible (532 nm) and UV (308 nm) flash photolysis of trans-[CpMo(CO)₃]₂ (Cp = η⁵-C₅H₅), in n-heptane solution, at room temperature. With visible irradiation, the primary photoproducts observed, on this time scale, are CpMo(CO)₃ (major) and gauche-[CpMo(CO)₃]₂. The CpMo(CO)₃ radical dimerizes (k₂ = 3(±1) x 10⁹ M^-1 s^-1) to form both trans- and gauche-[CpMo(CO)₃]₂. The gauche-[CpMo(CO)₃]₂ isomer decays (k = 2(±0.5) x 10² s^-1 to the more stable trans isomer. Upon UV flash photolysis the CO-loss intermediate, Cp₂Mo₂(CO)₅, is observed as a primary photoproduct together with the CpMo(CO)₃ radical and gauche-[CpMo(CO)₃]₂.

Original language	English
Pages (from-to)	1503-1506
Number of pages	4
Journal	Organometallics
Volume	14
Issue number	3
DOIs	https://doi.org/10.1021/om00003a060
Publication status	Published - Mar 1995
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Photochemistry of [CpMo(CO)3]2. Direct Detection and Kinetics of the Radical CpMo(CO)3 in n-Heptane Solution at Room Temperature by Fast Time-Resolved Infrared Spectroscopy",

abstract = "Fast (nanosecond) time-resolved infrared spectroscopy has been used to follow the visible (532 nm) and UV (308 nm) flash photolysis of trans-[CpMo(CO)3]2 (Cp = η5-C5H5), in n-heptane solution, at room temperature. With visible irradiation, the primary photoproducts observed, on this time scale, are CpMo(CO)3 (major) and gauche-[CpMo(CO)3]2. The CpMo(CO)3 radical dimerizes (k2 = 3(±1) x 109 M-1 s-1) to form both trans- and gauche-[CpMo(CO)3]2. The gauche-[CpMo(CO)3]2 isomer decays (k = 2(±0.5) x 102 s-1 to the more stable trans isomer. Upon UV flash photolysis the CO-loss intermediate, Cp2Mo2(CO)5, is observed as a primary photoproduct together with the CpMo(CO)3 radical and gauche-[CpMo(CO)3]2.",

author = "Jonas Peters and George, {Michael W.} and Turner, {James J.}",

year = "1995",

month = mar,

doi = "10.1021/om00003a060",

language = "English",

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pages = "1503--1506",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - Photochemistry of [CpMo(CO)3]2. Direct Detection and Kinetics of the Radical CpMo(CO)3 in n-Heptane Solution at Room Temperature by Fast Time-Resolved Infrared Spectroscopy

AU - Peters, Jonas

AU - George, Michael W.

AU - Turner, James J.

PY - 1995/3

Y1 - 1995/3

N2 - Fast (nanosecond) time-resolved infrared spectroscopy has been used to follow the visible (532 nm) and UV (308 nm) flash photolysis of trans-[CpMo(CO)3]2 (Cp = η5-C5H5), in n-heptane solution, at room temperature. With visible irradiation, the primary photoproducts observed, on this time scale, are CpMo(CO)3 (major) and gauche-[CpMo(CO)3]2. The CpMo(CO)3 radical dimerizes (k2 = 3(±1) x 109 M-1 s-1) to form both trans- and gauche-[CpMo(CO)3]2. The gauche-[CpMo(CO)3]2 isomer decays (k = 2(±0.5) x 102 s-1 to the more stable trans isomer. Upon UV flash photolysis the CO-loss intermediate, Cp2Mo2(CO)5, is observed as a primary photoproduct together with the CpMo(CO)3 radical and gauche-[CpMo(CO)3]2.

AB - Fast (nanosecond) time-resolved infrared spectroscopy has been used to follow the visible (532 nm) and UV (308 nm) flash photolysis of trans-[CpMo(CO)3]2 (Cp = η5-C5H5), in n-heptane solution, at room temperature. With visible irradiation, the primary photoproducts observed, on this time scale, are CpMo(CO)3 (major) and gauche-[CpMo(CO)3]2. The CpMo(CO)3 radical dimerizes (k2 = 3(±1) x 109 M-1 s-1) to form both trans- and gauche-[CpMo(CO)3]2. The gauche-[CpMo(CO)3]2 isomer decays (k = 2(±0.5) x 102 s-1 to the more stable trans isomer. Upon UV flash photolysis the CO-loss intermediate, Cp2Mo2(CO)5, is observed as a primary photoproduct together with the CpMo(CO)3 radical and gauche-[CpMo(CO)3]2.

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JO - Organometallics

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Photochemistry of [CpMo(CO)₃]₂. Direct Detection and Kinetics of the Radical CpMo(CO)₃ in n-Heptane Solution at Room Temperature by Fast Time-Resolved Infrared Spectroscopy

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