Stereoretentive Ligand Exchange Reactions of N‑Fused Porphyrin Ruthenium(II) Complexes

The ligand exchange reactions of the ruthenium­(II) complex of N-fused tetraphenylporphyrin, Ru­(NFp)­(CO)2Cl (2), with various anions were investigated. The chloride ligand of the isomers 2a–c was stereoretentively exchanged with bromide (Br–), iodide (I–), and acetate (AcO–) anions in toluene at 1...

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Published in:Inorganic chemistry 2017-11, Vol.56 (22), p.13842-13851
Main Authors: Matsuo, Hideaki, Toganoh, Motoki, Ishida, Masatoshi, Mori, Shigeki, Furuta, Hiroyuki
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container_end_page 13851
container_issue 22
container_start_page 13842
container_title Inorganic chemistry
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creator Matsuo, Hideaki
Toganoh, Motoki
Ishida, Masatoshi
Mori, Shigeki
Furuta, Hiroyuki
description The ligand exchange reactions of the ruthenium­(II) complex of N-fused tetraphenylporphyrin, Ru­(NFp)­(CO)2Cl (2), with various anions were investigated. The chloride ligand of the isomers 2a–c was stereoretentively exchanged with bromide (Br–), iodide (I–), and acetate (AcO–) anions in toluene at 100 °C, structures of which were confirmed by 1H NMR as well as single crystal X-ray diffraction analysis. The silver (AgOAc, AgOTf) and boron (NaBPh4) reagents also afforded the corresponding stereoretentive products. On the other hand, the reaction with NaBH4 afforded the hydride complex Ru­(NFp)­(CO)2H (7) with low stereospecificity, showing a higher reactivity of 2c than other isomers. The ligand dissociation mechanism was proposed with the help of theoretical calculations on the plausible five-coordinated intermediates.
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title Stereoretentive Ligand Exchange Reactions of N‑Fused Porphyrin Ruthenium(II) Complexes
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