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.
N1 - Publisher Copyright:
© 2019 Elsevier Inc.
PY - 2019/5
Y1 - 2019/5
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.
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U2 - 10.1016/j.jinorgbio.2019.03.003
DO - 10.1016/j.jinorgbio.2019.03.003
M3 - Article
C2 - 30856456
AN - SCOPUS:85062419790
SN - 0162-0134
VL - 194
SP - 160
EP - 169
JO - Journal of Inorganic Biochemistry
JF - Journal of Inorganic Biochemistry
ER -