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

152 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

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/ja017032m

Cite this

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",

pages = "11448--11455",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "38",

}

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.

UR - http://www.scopus.com/inward/record.url?scp=0037174457&partnerID=8YFLogxK

U2 - 10.1021/ja017032m

DO - 10.1021/ja017032m

M3 - Article

C2 - 12236759

AN - SCOPUS:0037174457

SN - 0002-7863

VL - 124

SP - 11448

EP - 11455

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 38

ER -