Interactions of acetamide and acrylamide with heme models

Synthesis, infrared spectra, and solid state molecular structures of five- and six-coordinate ferric porphyrin derivatives

Nan Xu, Ye Guan, Nhi Nguyen, Colin Lingafelt, Douglas R. Powell, George B. Richter-Addo

Research output: Contribution to journalArticle

Abstract

The amide functional group is a fundamental building block of proteins, but is also present in several industrial chemicals such as acetamide and acrylamide. Some acetamide derivatives are known to deplete cytoplasmic heme, and some acrylamide derivatives are known to cause porphyria and may activate soluble guanylyl cyclase through a heme-dependent mechanism. We have prepared a representative set of six-coordinate acetamide and acrylamide (L) complexes of iron porphyrins of the form [(por)Fe(L) 2 ]ClO 4 (por = TPP (tetraphenylporphyrinato dianion), T(p-OMe)PP (tetrakis(p-methoxyphenyl)porphyrinato dianion)) in 76–83% yields. We have also prepared the five-coordinate derivatives [(OEP)Fe(L)]ClO 4 (OEP = octaethylporphyrinato dianion) in 68–75% yields. These compounds were characterized by IR spectroscopy and by single-crystal X-ray crystallography. The molecular structures reveal the monodentate O-binding of the acetamide and acrylamide ligands to the ferric centers, with variable H-bonding exhibited between the acetamide/acrylamide –NH 2 moieties and the perchlorate anions. The five-coordinate OEP derivatives exhibit a π-π stacking of their porphyrin macrocycles, with the acetamide complex in the Class I and the acrylamide complex in the Class S groups. These compounds represent the first structurally characterized acetamide and acrylamide adducts of iron porphyrins. Reactions of the six-coordinate derivatives with NO result in the nitrosyl [(por)Fe(NO)(L)]ClO 4 derivatives that have been characterized by IR spectroscopy.

Original languageEnglish (US)
Pages (from-to)160-169
Number of pages10
JournalJournal of Inorganic Biochemistry
Volume194
DOIs
StatePublished - May 1 2019

Fingerprint

Acrylamide
Porphyrins
Molecular Structure
Heme
Molecular structure
Infrared radiation
Derivatives
Infrared spectroscopy
Spectrum Analysis
Iron
Industrial chemicals
Porphyrias
Guanylate Cyclase
X ray crystallography
X Ray Crystallography
acetamide
Amides
Functional groups
Anions
Single crystals

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Inorganic Chemistry

Cite this

@article{ec11a76b098744f7846de1b5058751c4,
title = "Interactions of acetamide and acrylamide with heme models: Synthesis, infrared spectra, and solid state molecular structures of five- and six-coordinate ferric porphyrin derivatives",
abstract = "The amide functional group is a fundamental building block of proteins, but is also present in several industrial chemicals such as acetamide and acrylamide. Some acetamide derivatives are known to deplete cytoplasmic heme, and some acrylamide derivatives are known to cause porphyria and may activate soluble guanylyl cyclase through a heme-dependent mechanism. We have prepared a representative set of six-coordinate acetamide and acrylamide (L) complexes of iron porphyrins of the form [(por)Fe(L) 2 ]ClO 4 (por = TPP (tetraphenylporphyrinato dianion), T(p-OMe)PP (tetrakis(p-methoxyphenyl)porphyrinato dianion)) in 76–83{\%} yields. We have also prepared the five-coordinate derivatives [(OEP)Fe(L)]ClO 4 (OEP = octaethylporphyrinato dianion) in 68–75{\%} yields. These compounds were characterized by IR spectroscopy and by single-crystal X-ray crystallography. The molecular structures reveal the monodentate O-binding of the acetamide and acrylamide ligands to the ferric centers, with variable H-bonding exhibited between the acetamide/acrylamide –NH 2 moieties and the perchlorate anions. The five-coordinate OEP derivatives exhibit a π-π stacking of their porphyrin macrocycles, with the acetamide complex in the Class I and the acrylamide complex in the Class S groups. These compounds represent the first structurally characterized acetamide and acrylamide adducts of iron porphyrins. Reactions of the six-coordinate derivatives with NO result in the nitrosyl [(por)Fe(NO)(L)]ClO 4 derivatives that have been characterized by IR spectroscopy.",
author = "Nan Xu and Ye Guan and Nhi Nguyen and Colin Lingafelt and Powell, {Douglas R.} and Richter-Addo, {George B.}",
year = "2019",
month = "5",
day = "1",
doi = "10.1016/j.jinorgbio.2019.03.003",
language = "English (US)",
volume = "194",
pages = "160--169",
journal = "Journal of Inorganic Biochemistry",
issn = "0162-0134",
publisher = "Elsevier Inc.",

}

Interactions of acetamide and acrylamide with heme models : Synthesis, infrared spectra, and solid state molecular structures of five- and six-coordinate ferric porphyrin derivatives. / Xu, Nan; Guan, Ye; Nguyen, Nhi; Lingafelt, Colin; Powell, Douglas R.; Richter-Addo, George B.

In: Journal of Inorganic Biochemistry, Vol. 194, 01.05.2019, p. 160-169.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Interactions of acetamide and acrylamide with heme models

T2 - Synthesis, infrared spectra, and solid state molecular structures of five- and six-coordinate ferric porphyrin derivatives

AU - Xu, Nan

AU - Guan, Ye

AU - Nguyen, Nhi

AU - Lingafelt, Colin

AU - Powell, Douglas R.

AU - Richter-Addo, George B.

PY - 2019/5/1

Y1 - 2019/5/1

N2 - The amide functional group is a fundamental building block of proteins, but is also present in several industrial chemicals such as acetamide and acrylamide. Some acetamide derivatives are known to deplete cytoplasmic heme, and some acrylamide derivatives are known to cause porphyria and may activate soluble guanylyl cyclase through a heme-dependent mechanism. We have prepared a representative set of six-coordinate acetamide and acrylamide (L) complexes of iron porphyrins of the form [(por)Fe(L) 2 ]ClO 4 (por = TPP (tetraphenylporphyrinato dianion), T(p-OMe)PP (tetrakis(p-methoxyphenyl)porphyrinato dianion)) in 76–83% yields. We have also prepared the five-coordinate derivatives [(OEP)Fe(L)]ClO 4 (OEP = octaethylporphyrinato dianion) in 68–75% yields. These compounds were characterized by IR spectroscopy and by single-crystal X-ray crystallography. The molecular structures reveal the monodentate O-binding of the acetamide and acrylamide ligands to the ferric centers, with variable H-bonding exhibited between the acetamide/acrylamide –NH 2 moieties and the perchlorate anions. The five-coordinate OEP derivatives exhibit a π-π stacking of their porphyrin macrocycles, with the acetamide complex in the Class I and the acrylamide complex in the Class S groups. These compounds represent the first structurally characterized acetamide and acrylamide adducts of iron porphyrins. Reactions of the six-coordinate derivatives with NO result in the nitrosyl [(por)Fe(NO)(L)]ClO 4 derivatives that have been characterized by IR spectroscopy.

AB - The amide functional group is a fundamental building block of proteins, but is also present in several industrial chemicals such as acetamide and acrylamide. Some acetamide derivatives are known to deplete cytoplasmic heme, and some acrylamide derivatives are known to cause porphyria and may activate soluble guanylyl cyclase through a heme-dependent mechanism. We have prepared a representative set of six-coordinate acetamide and acrylamide (L) complexes of iron porphyrins of the form [(por)Fe(L) 2 ]ClO 4 (por = TPP (tetraphenylporphyrinato dianion), T(p-OMe)PP (tetrakis(p-methoxyphenyl)porphyrinato dianion)) in 76–83% yields. We have also prepared the five-coordinate derivatives [(OEP)Fe(L)]ClO 4 (OEP = octaethylporphyrinato dianion) in 68–75% yields. These compounds were characterized by IR spectroscopy and by single-crystal X-ray crystallography. The molecular structures reveal the monodentate O-binding of the acetamide and acrylamide ligands to the ferric centers, with variable H-bonding exhibited between the acetamide/acrylamide –NH 2 moieties and the perchlorate anions. The five-coordinate OEP derivatives exhibit a π-π stacking of their porphyrin macrocycles, with the acetamide complex in the Class I and the acrylamide complex in the Class S groups. These compounds represent the first structurally characterized acetamide and acrylamide adducts of iron porphyrins. Reactions of the six-coordinate derivatives with NO result in the nitrosyl [(por)Fe(NO)(L)]ClO 4 derivatives that have been characterized by IR spectroscopy.

UR - http://www.scopus.com/inward/record.url?scp=85062419790&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85062419790&partnerID=8YFLogxK

U2 - 10.1016/j.jinorgbio.2019.03.003

DO - 10.1016/j.jinorgbio.2019.03.003

M3 - Article

VL - 194

SP - 160

EP - 169

JO - Journal of Inorganic Biochemistry

JF - Journal of Inorganic Biochemistry

SN - 0162-0134

ER -