Methodology to determine the NMR chemical shifts of carbon atoms with radical character: A case of low-spin bis(tert-butylisocyanide) complex of (meso-tetrapropylporphyrinato)iron(III)

Yuka Niibori; Akira Ikezaki; Mikio Nakamura

doi:10.1016/j.inoche.2011.05.049

Methodology to determine the NMR chemical shifts of carbon atoms with radical character: A case of low-spin bis(tert-butylisocyanide) complex of (meso-tetrapropylporphyrinato)iron(III)

Yuka Niibori, Akira Ikezaki, Mikio Nakamura

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

Paramagnetic metal complexes sometimes exhibit no appreciable ¹³C NMR signals due to the short relaxation time. By making use of the fast self-exchange electron transfer between paramagnetic [Fe ^III(TPrP)(^tBuNC)₂]ClO₄ and the corresponding diamagnetic [Fe^II(TPrP)(^tBuNC)₂], we have determined the chemical shifts of the carbon atoms that exhibit no signals due to the considerable amount of spin density. We have also determined the spin density of the meso carbon atom in [Fe^III(TPrP)( ^tBuNC)₂]ClO₄ to be 0.076, which is to our knowledge the largest among all the low-spin iron(III) porphyrin complexes reported previously. This method is applicable to all the low-spin iron(III) porphyrinoids if the corresponding diamagnetic complexes are available.

Original language	English
Pages (from-to)	1469-1474
Number of pages	6
Journal	Inorganic Chemistry Communications
Volume	14
Issue number	9
DOIs	https://doi.org/10.1016/j.inoche.2011.05.049
Publication status	Published - 2011 Sept
Externally published	Yes

Keywords

C NMR
Electron configuration
Iron porphyrin
Self-exchange electron transfer
Spin density

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.inoche.2011.05.049

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Methodology to determine the NMR chemical shifts of carbon atoms with radical character: A case of low-spin bis(tert-butylisocyanide) complex of (meso-tetrapropylporphyrinato)iron(III). / Niibori, Yuka; Ikezaki, Akira; Nakamura, Mikio.
In: Inorganic Chemistry Communications, Vol. 14, No. 9, 09.2011, p. 1469-1474.

Research output: Contribution to journal › Article › peer-review

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title = "Methodology to determine the NMR chemical shifts of carbon atoms with radical character: A case of low-spin bis(tert-butylisocyanide) complex of (meso-tetrapropylporphyrinato)iron(III)",

abstract = "Paramagnetic metal complexes sometimes exhibit no appreciable 13C NMR signals due to the short relaxation time. By making use of the fast self-exchange electron transfer between paramagnetic [Fe III(TPrP)(tBuNC)2]ClO4 and the corresponding diamagnetic [FeII(TPrP)(tBuNC)2], we have determined the chemical shifts of the carbon atoms that exhibit no signals due to the considerable amount of spin density. We have also determined the spin density of the meso carbon atom in [FeIII(TPrP)( tBuNC)2]ClO4 to be 0.076, which is to our knowledge the largest among all the low-spin iron(III) porphyrin complexes reported previously. This method is applicable to all the low-spin iron(III) porphyrinoids if the corresponding diamagnetic complexes are available.",

keywords = "C NMR, Electron configuration, Iron porphyrin, Self-exchange electron transfer, Spin density",

author = "Yuka Niibori and Akira Ikezaki and Mikio Nakamura",

note = "Funding Information: This work was supported by the Grant-in-Aid for Scientific Research (No. 22550157 ) from Ministry of Education, Culture, Sports, Science and Technology, Japan .",

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AU - Niibori, Yuka

AU - Ikezaki, Akira

AU - Nakamura, Mikio

N1 - Funding Information: This work was supported by the Grant-in-Aid for Scientific Research (No. 22550157 ) from Ministry of Education, Culture, Sports, Science and Technology, Japan .

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N2 - Paramagnetic metal complexes sometimes exhibit no appreciable 13C NMR signals due to the short relaxation time. By making use of the fast self-exchange electron transfer between paramagnetic [Fe III(TPrP)(tBuNC)2]ClO4 and the corresponding diamagnetic [FeII(TPrP)(tBuNC)2], we have determined the chemical shifts of the carbon atoms that exhibit no signals due to the considerable amount of spin density. We have also determined the spin density of the meso carbon atom in [FeIII(TPrP)( tBuNC)2]ClO4 to be 0.076, which is to our knowledge the largest among all the low-spin iron(III) porphyrin complexes reported previously. This method is applicable to all the low-spin iron(III) porphyrinoids if the corresponding diamagnetic complexes are available.

AB - Paramagnetic metal complexes sometimes exhibit no appreciable 13C NMR signals due to the short relaxation time. By making use of the fast self-exchange electron transfer between paramagnetic [Fe III(TPrP)(tBuNC)2]ClO4 and the corresponding diamagnetic [FeII(TPrP)(tBuNC)2], we have determined the chemical shifts of the carbon atoms that exhibit no signals due to the considerable amount of spin density. We have also determined the spin density of the meso carbon atom in [FeIII(TPrP)( tBuNC)2]ClO4 to be 0.076, which is to our knowledge the largest among all the low-spin iron(III) porphyrin complexes reported previously. This method is applicable to all the low-spin iron(III) porphyrinoids if the corresponding diamagnetic complexes are available.

KW - C NMR

KW - Electron configuration

KW - Iron porphyrin

KW - Self-exchange electron transfer

KW - Spin density

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Methodology to determine the NMR chemical shifts of carbon atoms with radical character: A case of low-spin bis(tert-butylisocyanide) complex of (meso-tetrapropylporphyrinato)iron(III)

Abstract

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