TY - JOUR
T1 - Stereoretentive Ligand Exchange Reactions of N-Fused Porphyrin Ruthenium(II) Complexes
AU - Matsuo, Hideaki
AU - Toganoh, Motoki
AU - Ishida, Masatoshi
AU - Mori, Shigeki
AU - Furuta, Hiroyuki
N1 - Funding Information:
The work was supported by the Grant-in-Aid (no. 15K13646 to H.F.; 16K05700 and 17H05377 to M.I.) from the Ministry of Education, Culture, Sports, Science and Technology of Japan. The financial support from a bilateral program between JSPS and the National Research Foundation (NRF) of South Africa is also acknowledged.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/11/20
Y1 - 2017/11/20
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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U2 - 10.1021/acs.inorgchem.7b01972
DO - 10.1021/acs.inorgchem.7b01972
M3 - Article
C2 - 28952311
AN - SCOPUS:85034591101
SN - 0020-1669
VL - 56
SP - 13842
EP - 13851
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 22
ER -