N-fused pentaphyrins and their rhodium complexes: Oxidation-induced rhodium rearrangement

Shigeki Mori, Ji Young Shin, Soji Shimizu, Fumiaki Ishikawa, Hiroyuki Furuta, Atsuhiro Osuka

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

meso-Aryl-substituted pentaphyrins were isolated in the modified Rothemund-Lindsey porphyrin synthesis as a 22-π-electron N-fused pentaphyrin ([22]NFP5) and a 24-π-electron N-fuscd pentaphyrin ([24]NFP 5), which were reversibly interconvertible by means of two-electron reduction with NaBH4 or two-electron oxidation with dichlorodicyanobenzoquinone (DDQ). Judging from 1H NMR data, [22]NFP5 is aromatic and possesses a diatropic ring current, while [24]NFP5 exhibits partial anti-aromatic character. Metalation of [22]NFP5 1 with a rhodium(I) salt led to isolation of rhodium complexes 9 and 10, whose structures were unambiguously characterized by X-ray diffraction analyses and were assigned as conjugated 24-π and 22-π electronic systems, respectively. In the rhodium(I) metalation of 1, the complex 9 was a major product at 20 °C, but the complex 10 became preferential at 55 °C. Upon treatment with DDQ, compound 9 was converted to 10 with an unprecedented rearrangement of the rhodium atom.

Original languageEnglish
Pages (from-to)2417-2425
Number of pages9
JournalChemistry - A European Journal
Volume11
Issue number8
DOIs
Publication statusPublished - Apr 8 2005

Fingerprint

Rhodium
Oxidation
Electrons
Porphyrins
Salts
Nuclear magnetic resonance
X ray diffraction
Atoms
dichlorodicyanobenzoquinone

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

N-fused pentaphyrins and their rhodium complexes : Oxidation-induced rhodium rearrangement. / Mori, Shigeki; Shin, Ji Young; Shimizu, Soji; Ishikawa, Fumiaki; Furuta, Hiroyuki; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 11, No. 8, 08.04.2005, p. 2417-2425.

Research output: Contribution to journalArticle

Mori, Shigeki ; Shin, Ji Young ; Shimizu, Soji ; Ishikawa, Fumiaki ; Furuta, Hiroyuki ; Osuka, Atsuhiro. / N-fused pentaphyrins and their rhodium complexes : Oxidation-induced rhodium rearrangement. In: Chemistry - A European Journal. 2005 ; Vol. 11, No. 8. pp. 2417-2425.
@article{6e1764c4b31c478584458ad208db3a88,
title = "N-fused pentaphyrins and their rhodium complexes: Oxidation-induced rhodium rearrangement",
abstract = "meso-Aryl-substituted pentaphyrins were isolated in the modified Rothemund-Lindsey porphyrin synthesis as a 22-π-electron N-fused pentaphyrin ([22]NFP5) and a 24-π-electron N-fuscd pentaphyrin ([24]NFP 5), which were reversibly interconvertible by means of two-electron reduction with NaBH4 or two-electron oxidation with dichlorodicyanobenzoquinone (DDQ). Judging from 1H NMR data, [22]NFP5 is aromatic and possesses a diatropic ring current, while [24]NFP5 exhibits partial anti-aromatic character. Metalation of [22]NFP5 1 with a rhodium(I) salt led to isolation of rhodium complexes 9 and 10, whose structures were unambiguously characterized by X-ray diffraction analyses and were assigned as conjugated 24-π and 22-π electronic systems, respectively. In the rhodium(I) metalation of 1, the complex 9 was a major product at 20 °C, but the complex 10 became preferential at 55 °C. Upon treatment with DDQ, compound 9 was converted to 10 with an unprecedented rearrangement of the rhodium atom.",
author = "Shigeki Mori and Shin, {Ji Young} and Soji Shimizu and Fumiaki Ishikawa and Hiroyuki Furuta and Atsuhiro Osuka",
year = "2005",
month = "4",
day = "8",
doi = "10.1002/chem.200401042",
language = "English",
volume = "11",
pages = "2417--2425",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "8",

}

TY - JOUR

T1 - N-fused pentaphyrins and their rhodium complexes

T2 - Oxidation-induced rhodium rearrangement

AU - Mori, Shigeki

AU - Shin, Ji Young

AU - Shimizu, Soji

AU - Ishikawa, Fumiaki

AU - Furuta, Hiroyuki

AU - Osuka, Atsuhiro

PY - 2005/4/8

Y1 - 2005/4/8

N2 - meso-Aryl-substituted pentaphyrins were isolated in the modified Rothemund-Lindsey porphyrin synthesis as a 22-π-electron N-fused pentaphyrin ([22]NFP5) and a 24-π-electron N-fuscd pentaphyrin ([24]NFP 5), which were reversibly interconvertible by means of two-electron reduction with NaBH4 or two-electron oxidation with dichlorodicyanobenzoquinone (DDQ). Judging from 1H NMR data, [22]NFP5 is aromatic and possesses a diatropic ring current, while [24]NFP5 exhibits partial anti-aromatic character. Metalation of [22]NFP5 1 with a rhodium(I) salt led to isolation of rhodium complexes 9 and 10, whose structures were unambiguously characterized by X-ray diffraction analyses and were assigned as conjugated 24-π and 22-π electronic systems, respectively. In the rhodium(I) metalation of 1, the complex 9 was a major product at 20 °C, but the complex 10 became preferential at 55 °C. Upon treatment with DDQ, compound 9 was converted to 10 with an unprecedented rearrangement of the rhodium atom.

AB - meso-Aryl-substituted pentaphyrins were isolated in the modified Rothemund-Lindsey porphyrin synthesis as a 22-π-electron N-fused pentaphyrin ([22]NFP5) and a 24-π-electron N-fuscd pentaphyrin ([24]NFP 5), which were reversibly interconvertible by means of two-electron reduction with NaBH4 or two-electron oxidation with dichlorodicyanobenzoquinone (DDQ). Judging from 1H NMR data, [22]NFP5 is aromatic and possesses a diatropic ring current, while [24]NFP5 exhibits partial anti-aromatic character. Metalation of [22]NFP5 1 with a rhodium(I) salt led to isolation of rhodium complexes 9 and 10, whose structures were unambiguously characterized by X-ray diffraction analyses and were assigned as conjugated 24-π and 22-π electronic systems, respectively. In the rhodium(I) metalation of 1, the complex 9 was a major product at 20 °C, but the complex 10 became preferential at 55 °C. Upon treatment with DDQ, compound 9 was converted to 10 with an unprecedented rearrangement of the rhodium atom.

UR - http://www.scopus.com/inward/record.url?scp=17444365847&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=17444365847&partnerID=8YFLogxK

U2 - 10.1002/chem.200401042

DO - 10.1002/chem.200401042

M3 - Article

C2 - 15696580

AN - SCOPUS:17444365847

VL - 11

SP - 2417

EP - 2425

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 8

ER -