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Article Abstract
Three possible isomers of N-fused tetraphenylporphyrin ruthenium complexes, Ru(NFTPp)Cl(CO)2 (2a-c), were isolated and fully characterized by NMR, IR, CV, UV-vis-NIR absorption, and X-ray crystallographic analyses. Each isomer was stable at ambient conditions and isomerization among 2a-c occurred at elevated temperature both in solution and in a solid state, through the intramolecular rotational pathways. Electronic structures of 2a-c were analyzed in detail by DFT study to reveal appreciable differences in the interaction between the NFTPp ligand and the Ru-Cl moiety.
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Stereoretentive Ligand Exchange Reactions of N-Fused Porphyrin Ruthenium(II) Complexes.
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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.
The ligand exchange reactions of the ruthenium(II) complex of N-fused tetraphenylporphyrin, Ru(NFp)(CO)Cl (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 H NMR as well as single crystal X-ray diffraction analysis. The silver (AgOAc, AgOTf) and boron (NaBPh) reagents also afforded the corresponding stereoretentive products.
View Article and Find Full Text PDFSynthesis and isomerization of N-fused tetraphenylporphyrin ruthenium(II) complexes.
Inorg Chem
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Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
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Inorg Chem
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Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Fukuoka 819-0395, Japan.
The reactions of N-fused tetraphenylporphyrin (NFTPP, 1a) and its 21-substituted derivatives, 21-Br-NFTPP (1b), 21-NO(2)-NFTPP (1c), and 21-Bz-NFTPP (1d), with Mn(CO)(5)Br gave the manganese(I) tricarbonyl complexes bearing N-fused tetraphenylporphyrinato ligands (2a-d), respectively, in 46-99% yields. The complexes were characterized by mass, IR, (1)H and (13)C NMR spectroscopy, and the final structural proof was evident from the X-ray crystallographic analysis for 2a. The crystals of 2a·CH(2)Cl(2) belong to the monoclinic space group P2(1)/n (#14), with a = 15.
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J Org Chem
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Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
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Chem Commun (Camb)
September 2005
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 812-8581, Japan.
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