Stereochemistry of Cobalt Porphyrins. I. The Structure and Characterization of 2,3,7,8,12,13,17,18-Octaethylporphinatobis(3-methylpyridine)cobalt(II)

Robert G. Little; James A Ibers

doi:10.1021/ja00821a016

Stereochemistry of Cobalt Porphyrins. I. The Structure and Characterization of 2,3,7,8,12,13,17,18-Octaethylporphinatobis(3-methylpyridine)cobalt(II)

Robert G. Little, James A Ibers^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

69 Scopus citations

Abstract

The six-coordinate Co(II) porphyrin, Co(3-pic)₂(OEP) (3-pic = 3-picoline = 3-methylpyridine), has been prepared and characterized by a complete X-ray structural determination. The structure has been refined anisotropically to a final conventional R value (on F) of 0.036 based on 3628 values of F_o² above background. The complex crystallizes in the triclinic space group C_i¹-P1 with a = 10.187 (3) Å, b = 11.258 (4) Å, c = 9.753 (3) Å, α = 93.10 (2)°, β = 92.32 (2)°, γ = 113.28 (2)°, and Z = 1. Hence the molecule has a crystallographically imposed center of symmetry. The axial Co-N(3-pic) bond length of 2.386 (2) Å is long compared with the average equatorial Co-N bond length of 1.992 (1) Å. The lengthening of the axial bond is attributed to the occupancy of the d_z² orbital by a single unpaired electron.

Original language	English (US)
Pages (from-to)	4440-4446
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	96
Issue number	14
DOIs	https://doi.org/10.1021/ja00821a016
State	Published - Jul 1 1974

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Stereochemistry of Cobalt Porphyrins. I. The Structure and Characterization of 2,3,7,8,12,13,17,18-Octaethylporphinatobis(3-methylpyridine)cobalt(II)",

abstract = "The six-coordinate Co(II) porphyrin, Co(3-pic)2(OEP) (3-pic = 3-picoline = 3-methylpyridine), has been prepared and characterized by a complete X-ray structural determination. The structure has been refined anisotropically to a final conventional R value (on F) of 0.036 based on 3628 values of Fo2 above background. The complex crystallizes in the triclinic space group Ci1-P1 with a = 10.187 (3) {\AA}, b = 11.258 (4) {\AA}, c = 9.753 (3) {\AA}, α = 93.10 (2)°, β = 92.32 (2)°, γ = 113.28 (2)°, and Z = 1. Hence the molecule has a crystallographically imposed center of symmetry. The axial Co-N(3-pic) bond length of 2.386 (2) {\AA} is long compared with the average equatorial Co-N bond length of 1.992 (1) {\AA}. The lengthening of the axial bond is attributed to the occupancy of the dz2 orbital by a single unpaired electron.",

author = "Little, {Robert G.} and Ibers, {James A}",

year = "1974",

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doi = "10.1021/ja00821a016",

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T1 - Stereochemistry of Cobalt Porphyrins. I. The Structure and Characterization of 2,3,7,8,12,13,17,18-Octaethylporphinatobis(3-methylpyridine)cobalt(II)

AU - Little, Robert G.

AU - Ibers, James A

PY - 1974/7/1

Y1 - 1974/7/1

N2 - The six-coordinate Co(II) porphyrin, Co(3-pic)2(OEP) (3-pic = 3-picoline = 3-methylpyridine), has been prepared and characterized by a complete X-ray structural determination. The structure has been refined anisotropically to a final conventional R value (on F) of 0.036 based on 3628 values of Fo2 above background. The complex crystallizes in the triclinic space group Ci1-P1 with a = 10.187 (3) Å, b = 11.258 (4) Å, c = 9.753 (3) Å, α = 93.10 (2)°, β = 92.32 (2)°, γ = 113.28 (2)°, and Z = 1. Hence the molecule has a crystallographically imposed center of symmetry. The axial Co-N(3-pic) bond length of 2.386 (2) Å is long compared with the average equatorial Co-N bond length of 1.992 (1) Å. The lengthening of the axial bond is attributed to the occupancy of the dz2 orbital by a single unpaired electron.

AB - The six-coordinate Co(II) porphyrin, Co(3-pic)2(OEP) (3-pic = 3-picoline = 3-methylpyridine), has been prepared and characterized by a complete X-ray structural determination. The structure has been refined anisotropically to a final conventional R value (on F) of 0.036 based on 3628 values of Fo2 above background. The complex crystallizes in the triclinic space group Ci1-P1 with a = 10.187 (3) Å, b = 11.258 (4) Å, c = 9.753 (3) Å, α = 93.10 (2)°, β = 92.32 (2)°, γ = 113.28 (2)°, and Z = 1. Hence the molecule has a crystallographically imposed center of symmetry. The axial Co-N(3-pic) bond length of 2.386 (2) Å is long compared with the average equatorial Co-N bond length of 1.992 (1) Å. The lengthening of the axial bond is attributed to the occupancy of the dz2 orbital by a single unpaired electron.

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Stereochemistry of Cobalt Porphyrins. I. The Structure and Characterization of 2,3,7,8,12,13,17,18-Octaethylporphinatobis(3-methylpyridine)cobalt(II)

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