Spectroscopic studies of novel porphyrin-copper(II) and zinc(II) complexes that share the pinch-porphyrin family structure of iron(III) complex models of peroxidases

José Luis Gárate-Morales, Yasmi Reyes-Ortega, Cecilio Alvarez-Toledano, René Gutiérrez-Pérez, Daniel Ramírez-Rosales, Rafael Zamorano-Ulloa, Eduardo Basurto-Uribe, Julio Hernández-Díaz, Rosalinda Contreras

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Abstract

Six novel pinch-porphyrin complexes [(picdien)(protoporphyrinate dimethyl ester)]copper(II) (7), [(picdien)(mesoporphyrinate dimethyl ester)]copper(II) (8) and [(picdien)(deuteroporphyrinate dimethyl ester)]copper(II) (9), [(picdien)(protoporphyrinate dimethyl ester)]zinc(II) (13), [(picdien)(mesoporphyrinate dimethyl ester)]zinc(II) (14) and [(picdien)(deuteroporphyrinate dimethyl ester)]zinc(II) (15), were prepared from the corresponding free copper(II)-porphyrins (4-6), and zinc(II)-porphyrins (10-12) and picdien (N-(3H-imidazol-4-ylmethyl)-N′-{2-[(3H-imidazol-4-ylmethyl)-amino]-ethyl}- ethane-2,3-diamine). Spectroscopic studies show that complexes (7-9) and (13-15) have the pinch-porphyrin type structure previously found in iron(III) complex models of peroxidases. Complexes (7-9), were characterized by u.v.-vis., m.c.d., and e.s.r. spectroscopy. E.s.r. spectra of the copper parent compounds (4-6) at ca. 10-2-10-4 concentrations were typical of copper(II)-dimers. The addition of the picdien ligand broke up the dimers as detected by e.s.r. Compounds (7-9) are predominantly monomeric at ca. 10-3 M concentration. The presence of picdien in (7-9) distorts the porphyrin internal portion of the plane so as to make these four internal nitrogen atoms, coordinated to copper(II), e.s.r-distinguishable. MO and ligand field theories were used to characterize and to evaluate the directional covalence parameters of compounds (7-9). A non-fully axial, out-of-the-porphyrin-plane bonding was found for (7-9), similar to the bonding of the pinch-porphyrins-iron(III). However the in-plane distortion produced by the presence of the picdien ligand on copper(II) is significantly larger than in pinch-porphyrin-iron(III). The n.m.r. data show that the porphyrin-zinc(II) is the less strained and has the weakest bonded structure. The coordination number of the pinch-porphyrin with iron(III), copper(II) and zinc(II), is in all cases six.
Original languageAmerican English
Pages (from-to)906-917
Number of pages814
JournalTransition Metal Chemistry
DOIs
StatePublished - 1 Nov 2002

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Peroxidases
Porphyrins
Zinc
Copper
Iron
Esters
Ligands
Dimers
Copper compounds
Ethane
Diamines
Nitrogen
Spectroscopy
Atoms

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Gárate-Morales, José Luis ; Reyes-Ortega, Yasmi ; Alvarez-Toledano, Cecilio ; Gutiérrez-Pérez, René ; Ramírez-Rosales, Daniel ; Zamorano-Ulloa, Rafael ; Basurto-Uribe, Eduardo ; Hernández-Díaz, Julio ; Contreras, Rosalinda. / Spectroscopic studies of novel porphyrin-copper(II) and zinc(II) complexes that share the pinch-porphyrin family structure of iron(III) complex models of peroxidases. In: Transition Metal Chemistry. 2002 ; pp. 906-917.
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title = "Spectroscopic studies of novel porphyrin-copper(II) and zinc(II) complexes that share the pinch-porphyrin family structure of iron(III) complex models of peroxidases",
abstract = "Six novel pinch-porphyrin complexes [(picdien)(protoporphyrinate dimethyl ester)]copper(II) (7), [(picdien)(mesoporphyrinate dimethyl ester)]copper(II) (8) and [(picdien)(deuteroporphyrinate dimethyl ester)]copper(II) (9), [(picdien)(protoporphyrinate dimethyl ester)]zinc(II) (13), [(picdien)(mesoporphyrinate dimethyl ester)]zinc(II) (14) and [(picdien)(deuteroporphyrinate dimethyl ester)]zinc(II) (15), were prepared from the corresponding free copper(II)-porphyrins (4-6), and zinc(II)-porphyrins (10-12) and picdien (N-(3H-imidazol-4-ylmethyl)-N′-{2-[(3H-imidazol-4-ylmethyl)-amino]-ethyl}- ethane-2,3-diamine). Spectroscopic studies show that complexes (7-9) and (13-15) have the pinch-porphyrin type structure previously found in iron(III) complex models of peroxidases. Complexes (7-9), were characterized by u.v.-vis., m.c.d., and e.s.r. spectroscopy. E.s.r. spectra of the copper parent compounds (4-6) at ca. 10-2-10-4 concentrations were typical of copper(II)-dimers. The addition of the picdien ligand broke up the dimers as detected by e.s.r. Compounds (7-9) are predominantly monomeric at ca. 10-3 M concentration. The presence of picdien in (7-9) distorts the porphyrin internal portion of the plane so as to make these four internal nitrogen atoms, coordinated to copper(II), e.s.r-distinguishable. MO and ligand field theories were used to characterize and to evaluate the directional covalence parameters of compounds (7-9). A non-fully axial, out-of-the-porphyrin-plane bonding was found for (7-9), similar to the bonding of the pinch-porphyrins-iron(III). However the in-plane distortion produced by the presence of the picdien ligand on copper(II) is significantly larger than in pinch-porphyrin-iron(III). The n.m.r. data show that the porphyrin-zinc(II) is the less strained and has the weakest bonded structure. The coordination number of the pinch-porphyrin with iron(III), copper(II) and zinc(II), is in all cases six.",
author = "G{\'a}rate-Morales, {Jos{\'e} Luis} and Yasmi Reyes-Ortega and Cecilio Alvarez-Toledano and Ren{\'e} Guti{\'e}rrez-P{\'e}rez and Daniel Ram{\'i}rez-Rosales and Rafael Zamorano-Ulloa and Eduardo Basurto-Uribe and Julio Hern{\'a}ndez-D{\'i}az and Rosalinda Contreras",
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doi = "10.1023/A:1021377006278",
language = "American English",
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Spectroscopic studies of novel porphyrin-copper(II) and zinc(II) complexes that share the pinch-porphyrin family structure of iron(III) complex models of peroxidases. / Gárate-Morales, José Luis; Reyes-Ortega, Yasmi; Alvarez-Toledano, Cecilio; Gutiérrez-Pérez, René; Ramírez-Rosales, Daniel; Zamorano-Ulloa, Rafael; Basurto-Uribe, Eduardo; Hernández-Díaz, Julio; Contreras, Rosalinda.

In: Transition Metal Chemistry, 01.11.2002, p. 906-917.

Research output: Contribution to journalArticle

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T1 - Spectroscopic studies of novel porphyrin-copper(II) and zinc(II) complexes that share the pinch-porphyrin family structure of iron(III) complex models of peroxidases

AU - Gárate-Morales, José Luis

AU - Reyes-Ortega, Yasmi

AU - Alvarez-Toledano, Cecilio

AU - Gutiérrez-Pérez, René

AU - Ramírez-Rosales, Daniel

AU - Zamorano-Ulloa, Rafael

AU - Basurto-Uribe, Eduardo

AU - Hernández-Díaz, Julio

AU - Contreras, Rosalinda

PY - 2002/11/1

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N2 - Six novel pinch-porphyrin complexes [(picdien)(protoporphyrinate dimethyl ester)]copper(II) (7), [(picdien)(mesoporphyrinate dimethyl ester)]copper(II) (8) and [(picdien)(deuteroporphyrinate dimethyl ester)]copper(II) (9), [(picdien)(protoporphyrinate dimethyl ester)]zinc(II) (13), [(picdien)(mesoporphyrinate dimethyl ester)]zinc(II) (14) and [(picdien)(deuteroporphyrinate dimethyl ester)]zinc(II) (15), were prepared from the corresponding free copper(II)-porphyrins (4-6), and zinc(II)-porphyrins (10-12) and picdien (N-(3H-imidazol-4-ylmethyl)-N′-{2-[(3H-imidazol-4-ylmethyl)-amino]-ethyl}- ethane-2,3-diamine). Spectroscopic studies show that complexes (7-9) and (13-15) have the pinch-porphyrin type structure previously found in iron(III) complex models of peroxidases. Complexes (7-9), were characterized by u.v.-vis., m.c.d., and e.s.r. spectroscopy. E.s.r. spectra of the copper parent compounds (4-6) at ca. 10-2-10-4 concentrations were typical of copper(II)-dimers. The addition of the picdien ligand broke up the dimers as detected by e.s.r. Compounds (7-9) are predominantly monomeric at ca. 10-3 M concentration. The presence of picdien in (7-9) distorts the porphyrin internal portion of the plane so as to make these four internal nitrogen atoms, coordinated to copper(II), e.s.r-distinguishable. MO and ligand field theories were used to characterize and to evaluate the directional covalence parameters of compounds (7-9). A non-fully axial, out-of-the-porphyrin-plane bonding was found for (7-9), similar to the bonding of the pinch-porphyrins-iron(III). However the in-plane distortion produced by the presence of the picdien ligand on copper(II) is significantly larger than in pinch-porphyrin-iron(III). The n.m.r. data show that the porphyrin-zinc(II) is the less strained and has the weakest bonded structure. The coordination number of the pinch-porphyrin with iron(III), copper(II) and zinc(II), is in all cases six.

AB - Six novel pinch-porphyrin complexes [(picdien)(protoporphyrinate dimethyl ester)]copper(II) (7), [(picdien)(mesoporphyrinate dimethyl ester)]copper(II) (8) and [(picdien)(deuteroporphyrinate dimethyl ester)]copper(II) (9), [(picdien)(protoporphyrinate dimethyl ester)]zinc(II) (13), [(picdien)(mesoporphyrinate dimethyl ester)]zinc(II) (14) and [(picdien)(deuteroporphyrinate dimethyl ester)]zinc(II) (15), were prepared from the corresponding free copper(II)-porphyrins (4-6), and zinc(II)-porphyrins (10-12) and picdien (N-(3H-imidazol-4-ylmethyl)-N′-{2-[(3H-imidazol-4-ylmethyl)-amino]-ethyl}- ethane-2,3-diamine). Spectroscopic studies show that complexes (7-9) and (13-15) have the pinch-porphyrin type structure previously found in iron(III) complex models of peroxidases. Complexes (7-9), were characterized by u.v.-vis., m.c.d., and e.s.r. spectroscopy. E.s.r. spectra of the copper parent compounds (4-6) at ca. 10-2-10-4 concentrations were typical of copper(II)-dimers. The addition of the picdien ligand broke up the dimers as detected by e.s.r. Compounds (7-9) are predominantly monomeric at ca. 10-3 M concentration. The presence of picdien in (7-9) distorts the porphyrin internal portion of the plane so as to make these four internal nitrogen atoms, coordinated to copper(II), e.s.r-distinguishable. MO and ligand field theories were used to characterize and to evaluate the directional covalence parameters of compounds (7-9). A non-fully axial, out-of-the-porphyrin-plane bonding was found for (7-9), similar to the bonding of the pinch-porphyrins-iron(III). However the in-plane distortion produced by the presence of the picdien ligand on copper(II) is significantly larger than in pinch-porphyrin-iron(III). The n.m.r. data show that the porphyrin-zinc(II) is the less strained and has the weakest bonded structure. The coordination number of the pinch-porphyrin with iron(III), copper(II) and zinc(II), is in all cases six.

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