Photochemistry of Cr(CO)4(bpy) (bpy = 2,2′-bipyridine) studied by time-resolved infrared spectroscopy

Ian G. Virreis; Michael W. George; James J. Turner; Jonas Peters; Antonín Vlček

doi:10.1021/om960369q

Photochemistry of Cr(CO)₄(bpy) (bpy = 2,2′-bipyridine) studied by time-resolved infrared spectroscopy

Ian G. Virreis, Michael W. George, James J. Turner, Jonas Peters, Antonín Vlček

Research output: Journal Publication › Article › peer-review

32 Citations (Scopus)

Abstract

Employing time-resolved IR spectroscopy, we have demonstrated that, following photolysis of Cr(CO)₄-(bpy) (1) in CH₂Cl₂, the only detectablephotoproduct on the 50 ns time scale is the solvated CO-loss intermediate fac-Cr(CO)₃(bpy)(CH₂Cl₂) (2); this intermediate is formed following either MLCT (532 nm) or LF (355 nm) excitation. The rate of the back-reaction of 2 with CO has been measured (k₂ = 7.1 (±0.5) × 70⁶M^-1 s^-1); in the presence of PPh₃, the intermediate 2 reacts to produce fac-Cr(CO)₃-(bpy)(PPh₃) (3) exclusively (k₂ = 1.0(±0.5)× 1.0⁷ M^-1 s^-1). From UV/visible flash photolysis data, we conclude that this intermediate 2 is probably produced on a ps / subps time scale.

Original language	English
Pages (from-to)	4089-4092
Number of pages	4
Journal	Organometallics
Volume	15
Issue number	19
DOIs	https://doi.org/10.1021/om960369q
Publication status	Published - 17 Sept 1996
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{40276135e27b4a8d99105e9a1ac1f29c,

title = "Photochemistry of Cr(CO)4(bpy) (bpy = 2,2′-bipyridine) studied by time-resolved infrared spectroscopy",

abstract = "Employing time-resolved IR spectroscopy, we have demonstrated that, following photolysis of Cr(CO)4-(bpy) (1) in CH2Cl2, the only detectablephotoproduct on the 50 ns time scale is the solvated CO-loss intermediate fac-Cr(CO)3(bpy)(CH2Cl2) (2); this intermediate is formed following either MLCT (532 nm) or LF (355 nm) excitation. The rate of the back-reaction of 2 with CO has been measured (k2 = 7.1 (±0.5) × 706M-1 s-1); in the presence of PPh3, the intermediate 2 reacts to produce fac-Cr(CO)3-(bpy)(PPh3) (3) exclusively (k2 = 1.0(±0.5)× 1.07 M-1 s-1). From UV/visible flash photolysis data, we conclude that this intermediate 2 is probably produced on a ps / subps time scale.",

author = "Virreis, {Ian G.} and George, {Michael W.} and Turner, {James J.} and Jonas Peters and Anton{\'i}n Vl{\v c}ek",

year = "1996",

month = sep,

day = "17",

doi = "10.1021/om960369q",

language = "English",

volume = "15",

pages = "4089--4092",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Photochemistry of Cr(CO)4(bpy) (bpy = 2,2′-bipyridine) studied by time-resolved infrared spectroscopy

AU - Virreis, Ian G.

AU - George, Michael W.

AU - Turner, James J.

AU - Peters, Jonas

AU - Vlček, Antonín

PY - 1996/9/17

Y1 - 1996/9/17

N2 - Employing time-resolved IR spectroscopy, we have demonstrated that, following photolysis of Cr(CO)4-(bpy) (1) in CH2Cl2, the only detectablephotoproduct on the 50 ns time scale is the solvated CO-loss intermediate fac-Cr(CO)3(bpy)(CH2Cl2) (2); this intermediate is formed following either MLCT (532 nm) or LF (355 nm) excitation. The rate of the back-reaction of 2 with CO has been measured (k2 = 7.1 (±0.5) × 706M-1 s-1); in the presence of PPh3, the intermediate 2 reacts to produce fac-Cr(CO)3-(bpy)(PPh3) (3) exclusively (k2 = 1.0(±0.5)× 1.07 M-1 s-1). From UV/visible flash photolysis data, we conclude that this intermediate 2 is probably produced on a ps / subps time scale.

AB - Employing time-resolved IR spectroscopy, we have demonstrated that, following photolysis of Cr(CO)4-(bpy) (1) in CH2Cl2, the only detectablephotoproduct on the 50 ns time scale is the solvated CO-loss intermediate fac-Cr(CO)3(bpy)(CH2Cl2) (2); this intermediate is formed following either MLCT (532 nm) or LF (355 nm) excitation. The rate of the back-reaction of 2 with CO has been measured (k2 = 7.1 (±0.5) × 706M-1 s-1); in the presence of PPh3, the intermediate 2 reacts to produce fac-Cr(CO)3-(bpy)(PPh3) (3) exclusively (k2 = 1.0(±0.5)× 1.07 M-1 s-1). From UV/visible flash photolysis data, we conclude that this intermediate 2 is probably produced on a ps / subps time scale.

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DO - 10.1021/om960369q

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VL - 15

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JF - Organometallics

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ER -

Photochemistry of Cr(CO)₄(bpy) (bpy = 2,2′-bipyridine) studied by time-resolved infrared spectroscopy

Abstract

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