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Title: Aqueous solution photophysics and photochemistry of dihalo- and aquahalobis(ethylenediamine)rhodium(III). Effect of nonreacting amine ligands on excited-state halide dissociation and excited-state rearrangement

Abstract

Ligand field excitation of cis- and trans-(Rh(en)2X2) (X = Cl, Br) in acidic aqueous solution leads to halide photoaquation producing (Rh(en)2(H2O)X)S . Room-temperature phosphorescence lifetimes of the four dihalo complexes in aqueous solution were measured by using a mode-locked laser and time-correlated single-photon detection and found to be about 2 ns in each case. Excited-state halide dissociation and nonradiative deactivation rate constants were evaluated from a combination of the lifetimes and the photoaquation quantum yields. The halide dissociation rate constants range from 1.9 x 10Y (cis-dichloro) to 2.1 x 10X s (trans-dibromo) and are in all cases smaller (by a factor of 1.6-15) than the rate constants previously determined for the tetraammine and bis(1,3-propanediamine) analogues. Also described are the syntheses of the dithionate salts of trans- and cis-(Rh(en)2(H2O)X)S , and quantum yields for the cis/trans interconversion of each isomeric pair in aqueous solution at 25C are given.

Authors:
; ; ;
Publication Date:
Research Org.:
Royal Veterinary and Agricultural Univ., Frederiksberg C, Denmark
OSTI Identifier:
6163622
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 26:11
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; EXCITED STATES; PHOTOCHEMICAL REACTIONS; BROMINE COMPOUNDS; CHLORINE COMPOUNDS; RHODIUM COMPLEXES; AQUEOUS SOLUTIONS; CHEMICAL REACTION KINETICS; EXPERIMENTAL DATA; LIFETIME; LIGANDS; PHOTOCHEMISTRY; QUANTUM EFFICIENCY; CHEMICAL REACTIONS; CHEMISTRY; COMPLEXES; DATA; DISPERSIONS; EFFICIENCY; ENERGY LEVELS; HALOGEN COMPOUNDS; INFORMATION; KINETICS; MIXTURES; NUMERICAL DATA; ORGANIC COMPOUNDS; REACTION KINETICS; SOLUTIONS; TRANSITION ELEMENT COMPLEXES; 400500* - Photochemistry

Citation Formats

Skibsted, L H, Hancock, M P, Magde, D, and Sexton, D A. Aqueous solution photophysics and photochemistry of dihalo- and aquahalobis(ethylenediamine)rhodium(III). Effect of nonreacting amine ligands on excited-state halide dissociation and excited-state rearrangement. United States: N. p., 1987. Web. doi:10.1021/ic00258a015.
Skibsted, L H, Hancock, M P, Magde, D, & Sexton, D A. Aqueous solution photophysics and photochemistry of dihalo- and aquahalobis(ethylenediamine)rhodium(III). Effect of nonreacting amine ligands on excited-state halide dissociation and excited-state rearrangement. United States. https://doi.org/10.1021/ic00258a015
Skibsted, L H, Hancock, M P, Magde, D, and Sexton, D A. 1987. "Aqueous solution photophysics and photochemistry of dihalo- and aquahalobis(ethylenediamine)rhodium(III). Effect of nonreacting amine ligands on excited-state halide dissociation and excited-state rearrangement". United States. https://doi.org/10.1021/ic00258a015.
@article{osti_6163622,
title = {Aqueous solution photophysics and photochemistry of dihalo- and aquahalobis(ethylenediamine)rhodium(III). Effect of nonreacting amine ligands on excited-state halide dissociation and excited-state rearrangement},
author = {Skibsted, L H and Hancock, M P and Magde, D and Sexton, D A},
abstractNote = {Ligand field excitation of cis- and trans-(Rh(en)2X2) (X = Cl, Br) in acidic aqueous solution leads to halide photoaquation producing (Rh(en)2(H2O)X)S . Room-temperature phosphorescence lifetimes of the four dihalo complexes in aqueous solution were measured by using a mode-locked laser and time-correlated single-photon detection and found to be about 2 ns in each case. Excited-state halide dissociation and nonradiative deactivation rate constants were evaluated from a combination of the lifetimes and the photoaquation quantum yields. The halide dissociation rate constants range from 1.9 x 10Y (cis-dichloro) to 2.1 x 10X s (trans-dibromo) and are in all cases smaller (by a factor of 1.6-15) than the rate constants previously determined for the tetraammine and bis(1,3-propanediamine) analogues. Also described are the syntheses of the dithionate salts of trans- and cis-(Rh(en)2(H2O)X)S , and quantum yields for the cis/trans interconversion of each isomeric pair in aqueous solution at 25C are given.},
doi = {10.1021/ic00258a015},
url = {https://www.osti.gov/biblio/6163622}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 26:11,
place = {United States},
year = {Wed Jun 03 00:00:00 EDT 1987},
month = {Wed Jun 03 00:00:00 EDT 1987}
}