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

Hideaki Matsuo, Motoki Toganoh, Masatoshi Ishida, Shigeki Mori, Hiroyuki Furuta

Research output: Contribution to journalArticle

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Abstract

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.

Original languageEnglish
Pages (from-to)13842-13851
Number of pages10
JournalInorganic Chemistry
Volume56
Issue number22
DOIs
Publication statusPublished - Nov 20 2017

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Ruthenium
Porphyrins
porphyrins
ruthenium
Carbon Monoxide
Ligands
Isomers
ligands
Anions
isomers
anions
Boron
Toluene
Iodides
Bromides
Silver
Hydrides
X ray diffraction analysis
iodides
hydrides

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Stereoretentive Ligand Exchange Reactions of N-Fused Porphyrin Ruthenium(II) Complexes. / Matsuo, Hideaki; Toganoh, Motoki; Ishida, Masatoshi; Mori, Shigeki; Furuta, Hiroyuki.

In: Inorganic Chemistry, Vol. 56, No. 22, 20.11.2017, p. 13842-13851.

Research output: Contribution to journalArticle

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AU - Furuta, Hiroyuki

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N2 - 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.

AB - 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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