Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)3(PR3)]+ complexes and the properties of their triplet ligand-field excited states

Kazuhide Koike; Nobuaki Okoshi; Hisao Hori; Koji Takeuchi; Osamu Ishitani; Hideaki Tsubaki; Ian P. Clark; Michael W. George; Frank P.A. Johnson; James J. Turner

doi:10.1021/ja017032m

Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ complexes and the properties of their triplet ligand-field excited states

Kazuhide Koike, Nobuaki Okoshi, Hisao Hori, Koji Takeuchi, Osamu Ishitani, Hideaki Tsubaki, Ian P. Clark, Michael W. George, Frank P.A. Johnson, James J. Turner

Research output: Journal Publication › Article › peer-review

148 Citations (Scopus)

Abstract

We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X₂bpy)(CO)₃(PR₃)]⁺ complexes (1) and the properties of their triplet ligand-field (³LF) excited states. The reason for the photostability of the rhenium complexes [Re(X₂bpy)(CO)₃(py)]⁺ (3) and [Re(X₂bpy)(CO)₃Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X₂bpy)(CO)₂(PR₃) (CH₃CN)]⁺ (2). Isotope experiments clearly showed that the CO ligand trans to the PR₃ ligand was selectively substituted, The photochemical reactions proceeded via a dissociative mechanism from the ³LF excited state. The thermodynamical data for the ³LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer (³MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X₂bpy)(CO)₃(py)]⁺ (3) and [Re(X₂bpy)(CO)₃Cl] (4) indicated that the ³LF states of some 3- and 4-type complexes are probably accessible from the ³MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR₃, py, and Cl^- ligands.

Original language	English
Pages (from-to)	11448-11455
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	124
Issue number	38
DOIs	https://doi.org/10.1021/ja017032m
Publication status	Published - 25 Sept 2002
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja017032m

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Koike, K., Okoshi, N., Hori, H., Takeuchi, K., Ishitani, O., Tsubaki, H., Clark, I. P., George, M. W., Johnson, F. P. A., & Turner, J. J. (2002). Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ complexes and the properties of their triplet ligand-field excited states. Journal of the American Chemical Society, 124(38), 11448-11455. https://doi.org/10.1021/ja017032m

@article{ca01d6124ddf4459a7f7c66df5611790,

title = "Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)3(PR3)]+ complexes and the properties of their triplet ligand-field excited states",

abstract = "We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X2bpy)(CO)3(PR3)]+ complexes (1) and the properties of their triplet ligand-field (3LF) excited states. The reason for the photostability of the rhenium complexes [Re(X2bpy)(CO)3(py)]+ (3) and [Re(X2bpy)(CO)3Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X2bpy)(CO)2(PR3) (CH3CN)]+ (2). Isotope experiments clearly showed that the CO ligand trans to the PR3 ligand was selectively substituted, The photochemical reactions proceeded via a dissociative mechanism from the 3LF excited state. The thermodynamical data for the 3LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer (3MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X2bpy)(CO)3(py)]+ (3) and [Re(X2bpy)(CO)3Cl] (4) indicated that the 3LF states of some 3- and 4-type complexes are probably accessible from the 3MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR3, py, and Cl- ligands.",

author = "Kazuhide Koike and Nobuaki Okoshi and Hisao Hori and Koji Takeuchi and Osamu Ishitani and Hideaki Tsubaki and Clark, {Ian P.} and George, {Michael W.} and Johnson, {Frank P.A.} and Turner, {James J.}",

year = "2002",

month = sep,

day = "25",

doi = "10.1021/ja017032m",

language = "English",

volume = "124",

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Koike, K, Okoshi, N, Hori, H, Takeuchi, K, Ishitani, O, Tsubaki, H, Clark, IP, George, MW, Johnson, FPA & Turner, JJ 2002, 'Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ complexes and the properties of their triplet ligand-field excited states', Journal of the American Chemical Society, vol. 124, no. 38, pp. 11448-11455. https://doi.org/10.1021/ja017032m

Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ complexes and the properties of their triplet ligand-field excited states. / Koike, Kazuhide; Okoshi, Nobuaki; Hori, Hisao et al.
In: Journal of the American Chemical Society, Vol. 124, No. 38, 25.09.2002, p. 11448-11455.

Research output: Journal Publication › Article › peer-review

TY - JOUR

T1 - Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)3(PR3)]+ complexes and the properties of their triplet ligand-field excited states

AU - Koike, Kazuhide

AU - Okoshi, Nobuaki

AU - Hori, Hisao

AU - Takeuchi, Koji

AU - Ishitani, Osamu

AU - Tsubaki, Hideaki

AU - Clark, Ian P.

AU - George, Michael W.

AU - Johnson, Frank P.A.

AU - Turner, James J.

PY - 2002/9/25

Y1 - 2002/9/25

N2 - We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X2bpy)(CO)3(PR3)]+ complexes (1) and the properties of their triplet ligand-field (3LF) excited states. The reason for the photostability of the rhenium complexes [Re(X2bpy)(CO)3(py)]+ (3) and [Re(X2bpy)(CO)3Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X2bpy)(CO)2(PR3) (CH3CN)]+ (2). Isotope experiments clearly showed that the CO ligand trans to the PR3 ligand was selectively substituted, The photochemical reactions proceeded via a dissociative mechanism from the 3LF excited state. The thermodynamical data for the 3LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer (3MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X2bpy)(CO)3(py)]+ (3) and [Re(X2bpy)(CO)3Cl] (4) indicated that the 3LF states of some 3- and 4-type complexes are probably accessible from the 3MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR3, py, and Cl- ligands.

AB - We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X2bpy)(CO)3(PR3)]+ complexes (1) and the properties of their triplet ligand-field (3LF) excited states. The reason for the photostability of the rhenium complexes [Re(X2bpy)(CO)3(py)]+ (3) and [Re(X2bpy)(CO)3Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X2bpy)(CO)2(PR3) (CH3CN)]+ (2). Isotope experiments clearly showed that the CO ligand trans to the PR3 ligand was selectively substituted, The photochemical reactions proceeded via a dissociative mechanism from the 3LF excited state. The thermodynamical data for the 3LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer (3MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X2bpy)(CO)3(py)]+ (3) and [Re(X2bpy)(CO)3Cl] (4) indicated that the 3LF states of some 3- and 4-type complexes are probably accessible from the 3MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR3, py, and Cl- ligands.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 38

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Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)₃(PR₃)]⁺ complexes and the properties of their triplet ligand-field excited states

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