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

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

doi:10.1021/acs.inorgchem.7b01972

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

Inorg Chem. 2017 Nov 20;56(22):13842-13851. doi: 10.1021/acs.inorgchem.7b01972. Epub 2017 Sep 27.

Authors

Hideaki Matsuo¹, Motoki Toganoh¹, Masatoshi Ishida¹, Shigeki Mori², Hiroyuki Furuta¹

Affiliations

¹ Department of Chemistry and Biochemistry, Graduate School of Engineering, and the Center for Molecular Systems, Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
² Advanced Research Support Center, Ehime University , Matsuyama 790-8577, Japan.

PMID: 28952311
DOI: 10.1021/acs.inorgchem.7b01972

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.