Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes

Katrina M Miranda, Xianhui Bu, Ivan Lorković, Peter C. Ford

Research output: Contribution to journalArticle

105 Citations (Scopus)

Abstract

The synthesis, X-ray crystal structures, and some spectroscopic and chemical properties of the nitrosylruthenium(II) porphyrin complexes Ru(TPP) (NO) (ONO), Ru(TPP) (NO) (OH), Ru(OEP) (NO) (ONO), and Ru(OEP) (NO)-(OH) (TPP = tetraphenylporphyrinato dianion; OEP = octaethylporphyrinato dianion) derived from the analogous Ru(II) carbonyl complexes are reported. Also described are experiments which quantitatively demonstrate that N2O is formed as a product of the synthesis scheme and that NO serves as the principal oxidant in the transformation of N(II) to N(III). The two TPP complexes are isostructural and consist of columns of molecules stacked along the c axis. The two OEP complexes are also isostructural and can be considered as layers of OEP complexes stacked along the b axis with solvent molecules situated at the cavities between layers. The nitrite ions are coordinated in a unidentate fashion through the oxygen atom. Crystal data for Ru(TPP) (NO) (ONO) (1): M = 789.79, space group I4/m (No. 87), a = 13.6529(6) Å, c = 9.7904(5) Å, V = 1825.0(2) Å3, Z = 2, ρ = 1.437 g cm-3, purple bipyramid, 2θmax = 50.0°, R(F) = 4.87% for 86 parameters and 838 reflections with I > 2σ(I). Crystal data for Ru(TPP) (NO) (OH) (2): M = 760.79, space group I4/m (No. 87), a = 13.5423(4) Å, c = 9.7150-(4) Å, V= 1781.7(1) Å3, Z = 2, ρ = 1 .418 g cm-3, dark red plate, 2θmax = 50.0°, R(F) = 3.92% for 83 parameters and 811 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO)(ONO)·CH2Cl2 (3): M = 794.77, space group P21 (No. 4), a = 10.7687(2) Å, b = 21.0320(2) Å, c = 8.5936(2) Å, β= 102.683(1)°, V= 1898.85(6) Å3, Z = 2, ρ = 1.390 g cm-3, black plate, 2θmax = 50.0°, R(F) = 6.23% for 453 parameters and 4702 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO) (OH)·C2H5OH (4): M = 726.91, space group P21 (No. 4), a = 10.8474-(7) Ǎ, b = 21.002(1) Å, c = 8.3646(5) Å, β= 103.571(1)°, V= 1852.4(2) Å3, Z= 2, ρ = 1.303 g cm-3, brown plate, 2θmax = 45.0°, R(F) = 6.74% for 421 parameters and 3527 reflections with I > 2σ(I).

Original languageEnglish (US)
Pages (from-to)4838-4848
Number of pages11
JournalInorganic Chemistry
Volume36
Issue number21
StatePublished - 1997
Externally publishedYes

Fingerprint

Ruthenium
Porphyrins
porphyrins
ruthenium
Crystals
synthesis
crystals
Molecules
nitrites
Nitrites
Oxidants
chemical properties
Chemical properties
molecules
oxygen atoms
Crystal structure
Ions
Oxygen
X rays
Atoms

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes. / Miranda, Katrina M; Bu, Xianhui; Lorković, Ivan; Ford, Peter C.

In: Inorganic Chemistry, Vol. 36, No. 21, 1997, p. 4838-4848.

Research output: Contribution to journalArticle

Miranda, Katrina M ; Bu, Xianhui ; Lorković, Ivan ; Ford, Peter C. / Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes. In: Inorganic Chemistry. 1997 ; Vol. 36, No. 21. pp. 4838-4848.
@article{8e93f8df930a495289128b04bc84ae3a,
title = "Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes",
abstract = "The synthesis, X-ray crystal structures, and some spectroscopic and chemical properties of the nitrosylruthenium(II) porphyrin complexes Ru(TPP) (NO) (ONO), Ru(TPP) (NO) (OH), Ru(OEP) (NO) (ONO), and Ru(OEP) (NO)-(OH) (TPP = tetraphenylporphyrinato dianion; OEP = octaethylporphyrinato dianion) derived from the analogous Ru(II) carbonyl complexes are reported. Also described are experiments which quantitatively demonstrate that N2O is formed as a product of the synthesis scheme and that NO serves as the principal oxidant in the transformation of N(II) to N(III). The two TPP complexes are isostructural and consist of columns of molecules stacked along the c axis. The two OEP complexes are also isostructural and can be considered as layers of OEP complexes stacked along the b axis with solvent molecules situated at the cavities between layers. The nitrite ions are coordinated in a unidentate fashion through the oxygen atom. Crystal data for Ru(TPP) (NO) (ONO) (1): M = 789.79, space group I4/m (No. 87), a = 13.6529(6) {\AA}, c = 9.7904(5) {\AA}, V = 1825.0(2) {\AA}3, Z = 2, ρ = 1.437 g cm-3, purple bipyramid, 2θmax = 50.0°, R(F) = 4.87{\%} for 86 parameters and 838 reflections with I > 2σ(I). Crystal data for Ru(TPP) (NO) (OH) (2): M = 760.79, space group I4/m (No. 87), a = 13.5423(4) {\AA}, c = 9.7150-(4) {\AA}, V= 1781.7(1) {\AA}3, Z = 2, ρ = 1 .418 g cm-3, dark red plate, 2θmax = 50.0°, R(F) = 3.92{\%} for 83 parameters and 811 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO)(ONO)·CH2Cl2 (3): M = 794.77, space group P21 (No. 4), a = 10.7687(2) {\AA}, b = 21.0320(2) {\AA}, c = 8.5936(2) {\AA}, β= 102.683(1)°, V= 1898.85(6) {\AA}3, Z = 2, ρ = 1.390 g cm-3, black plate, 2θmax = 50.0°, R(F) = 6.23{\%} for 453 parameters and 4702 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO) (OH)·C2H5OH (4): M = 726.91, space group P21 (No. 4), a = 10.8474-(7) Ǎ, b = 21.002(1) {\AA}, c = 8.3646(5) {\AA}, β= 103.571(1)°, V= 1852.4(2) {\AA}3, Z= 2, ρ = 1.303 g cm-3, brown plate, 2θmax = 45.0°, R(F) = 6.74{\%} for 421 parameters and 3527 reflections with I > 2σ(I).",
author = "Miranda, {Katrina M} and Xianhui Bu and Ivan Lorković and Ford, {Peter C.}",
year = "1997",
language = "English (US)",
volume = "36",
pages = "4838--4848",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes

AU - Miranda, Katrina M

AU - Bu, Xianhui

AU - Lorković, Ivan

AU - Ford, Peter C.

PY - 1997

Y1 - 1997

N2 - The synthesis, X-ray crystal structures, and some spectroscopic and chemical properties of the nitrosylruthenium(II) porphyrin complexes Ru(TPP) (NO) (ONO), Ru(TPP) (NO) (OH), Ru(OEP) (NO) (ONO), and Ru(OEP) (NO)-(OH) (TPP = tetraphenylporphyrinato dianion; OEP = octaethylporphyrinato dianion) derived from the analogous Ru(II) carbonyl complexes are reported. Also described are experiments which quantitatively demonstrate that N2O is formed as a product of the synthesis scheme and that NO serves as the principal oxidant in the transformation of N(II) to N(III). The two TPP complexes are isostructural and consist of columns of molecules stacked along the c axis. The two OEP complexes are also isostructural and can be considered as layers of OEP complexes stacked along the b axis with solvent molecules situated at the cavities between layers. The nitrite ions are coordinated in a unidentate fashion through the oxygen atom. Crystal data for Ru(TPP) (NO) (ONO) (1): M = 789.79, space group I4/m (No. 87), a = 13.6529(6) Å, c = 9.7904(5) Å, V = 1825.0(2) Å3, Z = 2, ρ = 1.437 g cm-3, purple bipyramid, 2θmax = 50.0°, R(F) = 4.87% for 86 parameters and 838 reflections with I > 2σ(I). Crystal data for Ru(TPP) (NO) (OH) (2): M = 760.79, space group I4/m (No. 87), a = 13.5423(4) Å, c = 9.7150-(4) Å, V= 1781.7(1) Å3, Z = 2, ρ = 1 .418 g cm-3, dark red plate, 2θmax = 50.0°, R(F) = 3.92% for 83 parameters and 811 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO)(ONO)·CH2Cl2 (3): M = 794.77, space group P21 (No. 4), a = 10.7687(2) Å, b = 21.0320(2) Å, c = 8.5936(2) Å, β= 102.683(1)°, V= 1898.85(6) Å3, Z = 2, ρ = 1.390 g cm-3, black plate, 2θmax = 50.0°, R(F) = 6.23% for 453 parameters and 4702 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO) (OH)·C2H5OH (4): M = 726.91, space group P21 (No. 4), a = 10.8474-(7) Ǎ, b = 21.002(1) Å, c = 8.3646(5) Å, β= 103.571(1)°, V= 1852.4(2) Å3, Z= 2, ρ = 1.303 g cm-3, brown plate, 2θmax = 45.0°, R(F) = 6.74% for 421 parameters and 3527 reflections with I > 2σ(I).

AB - The synthesis, X-ray crystal structures, and some spectroscopic and chemical properties of the nitrosylruthenium(II) porphyrin complexes Ru(TPP) (NO) (ONO), Ru(TPP) (NO) (OH), Ru(OEP) (NO) (ONO), and Ru(OEP) (NO)-(OH) (TPP = tetraphenylporphyrinato dianion; OEP = octaethylporphyrinato dianion) derived from the analogous Ru(II) carbonyl complexes are reported. Also described are experiments which quantitatively demonstrate that N2O is formed as a product of the synthesis scheme and that NO serves as the principal oxidant in the transformation of N(II) to N(III). The two TPP complexes are isostructural and consist of columns of molecules stacked along the c axis. The two OEP complexes are also isostructural and can be considered as layers of OEP complexes stacked along the b axis with solvent molecules situated at the cavities between layers. The nitrite ions are coordinated in a unidentate fashion through the oxygen atom. Crystal data for Ru(TPP) (NO) (ONO) (1): M = 789.79, space group I4/m (No. 87), a = 13.6529(6) Å, c = 9.7904(5) Å, V = 1825.0(2) Å3, Z = 2, ρ = 1.437 g cm-3, purple bipyramid, 2θmax = 50.0°, R(F) = 4.87% for 86 parameters and 838 reflections with I > 2σ(I). Crystal data for Ru(TPP) (NO) (OH) (2): M = 760.79, space group I4/m (No. 87), a = 13.5423(4) Å, c = 9.7150-(4) Å, V= 1781.7(1) Å3, Z = 2, ρ = 1 .418 g cm-3, dark red plate, 2θmax = 50.0°, R(F) = 3.92% for 83 parameters and 811 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO)(ONO)·CH2Cl2 (3): M = 794.77, space group P21 (No. 4), a = 10.7687(2) Å, b = 21.0320(2) Å, c = 8.5936(2) Å, β= 102.683(1)°, V= 1898.85(6) Å3, Z = 2, ρ = 1.390 g cm-3, black plate, 2θmax = 50.0°, R(F) = 6.23% for 453 parameters and 4702 reflections with I > 2σ(I). Crystal data for Ru(OEP) (NO) (OH)·C2H5OH (4): M = 726.91, space group P21 (No. 4), a = 10.8474-(7) Ǎ, b = 21.002(1) Å, c = 8.3646(5) Å, β= 103.571(1)°, V= 1852.4(2) Å3, Z= 2, ρ = 1.303 g cm-3, brown plate, 2θmax = 45.0°, R(F) = 6.74% for 421 parameters and 3527 reflections with I > 2σ(I).

UR - http://www.scopus.com/inward/record.url?scp=0001240364&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001240364&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001240364

VL - 36

SP - 4838

EP - 4848

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 21

ER -