Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes

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

doi:10.1021/ic970065b

Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes

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

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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, 2θ_max = 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, 2θ_max = 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, 2θ_max = 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, 2θ_max = 45.0°, R(F) = 6.74% for 421 parameters and 3527 reflections with I > 2σ(I).

Original language	English (US)
Pages (from-to)	4838-4848
Number of pages	11
Journal	Inorganic Chemistry
Volume	36
Issue number	21
DOIs	https://doi.org/10.1021/ic970065b
State	Published - 1997
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@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 Lorkovi{\'c} and Ford, {Peter C.}",

year = "1997",

doi = "10.1021/ic970065b",

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).

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U2 - 10.1021/ic970065b

DO - 10.1021/ic970065b

M3 - Article

AN - SCOPUS:0001240364

SN - 0020-1669

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes

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