Synthesis and Characterization of Cobalt(II) N,N′‑Diphenylazodioxide Complexes

Kylin A. Emhoff; Lakshmi Balaraman; Sydney R. Simpson; Michael L. Stromyer; Haitham F. Kalil; James R. Beemiller; Philipp Sikatzki; Teya S. Eshelman; Ahmed M.H. Salem; Michael A. DeBord; Matthew J. Panzer; Wiley J. Youngs; W. Christropher Boyd

doi:10.1021/acsomega.8b01200

Synthesis and Characterization of Cobalt(II) N,N′‑Diphenylazodioxide Complexes

Kylin A. Emhoff, Lakshmi Balaraman, Sydney R. Simpson, Michael L. Stromyer, Haitham F. Kalil, James R. Beemiller, Philipp Sikatzki, Teya S. Eshelman, Ahmed M.H. Salem, Michael A. DeBord, Matthew J. Panzer, Wiley J. Youngs, W. Christropher Boyd

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

Abstract

Removal of chloride from CoCl ₂ with TlPF ₆ in acetonitrile, followed by addition of excess nitrosobenzene, yielded the eight-coordinate cobalt(II) complex salt [Co{Ph(O)NN(O)- Ph} ₄ ](PF ₆ ) ₂ , shown by single-crystal X-ray analysis to have a distorted tetragonal geometry. The analogous treatment of the bipyridyl complex Co(bpy)Cl ₂ yielded the mixed-ligand cobalt(II) complex salt [Co(bpy){Ph(O)NN(O)Ph} ₂ ](PF ₆ ) ₂ , whose singlecrystal X-ray structure displays a trigonal prismatic geometry, similar to that of the iron(II) cation in the previously known complex salt [Fe{Ph(O)NN(O)Ph} ₃ ](FeCl ₄ ) ₂ . The use of TlPF ₆ to generate solvated metal complex cations from chloride salts or chlorido complexes, followed by the addition of nitrosobenzene, is shown to be a useful synthetic strategy for the preparation of azodioxide complex cations with the noncoordinating, diamagnetic PF ₆ − counteranion. Coordination number appears to be more important than d electron count in determining the geometry and metal−ligand bond distances of diphenylazodioxide complexes.

Original language	American English
Journal	ACS Omega
Volume	3
DOIs	https://doi.org/10.1021/acsomega.8b01200
State	Published - Nov 27 2018

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Chemistry

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Synthesis and Characterization of Cobalt(II) NN DiphenylazodioxFinal published version, 1.21 MBLicense: CC BY
Synthesis and Characterization of Cobalt(II) NN DiphenylazodioxFinal published version, 1.21 MBLicense: CC BY

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@article{f9333f7f5136464ab108d9468abc5f95,

title = "Synthesis and Characterization of Cobalt(II) N,N′‑Diphenylazodioxide Complexes",

abstract = " Removal of chloride from CoCl 2 with TlPF 6 in acetonitrile, followed by addition of excess nitrosobenzene, yielded the eight-coordinate cobalt(II) complex salt [Co\{Ph(O)NN(O)- Ph\} 4 ](PF 6 ) 2 , shown by single-crystal X-ray analysis to have a distorted tetragonal geometry. The analogous treatment of the bipyridyl complex Co(bpy)Cl 2 yielded the mixed-ligand cobalt(II) complex salt [Co(bpy)\{Ph(O)NN(O)Ph\} 2 ](PF 6 ) 2 , whose singlecrystal X-ray structure displays a trigonal prismatic geometry, similar to that of the iron(II) cation in the previously known complex salt [Fe\{Ph(O)NN(O)Ph\} 3 ](FeCl 4 ) 2 . The use of TlPF 6 to generate solvated metal complex cations from chloride salts or chlorido complexes, followed by the addition of nitrosobenzene, is shown to be a useful synthetic strategy for the preparation of azodioxide complex cations with the noncoordinating, diamagnetic PF 6 − counteranion. Coordination number appears to be more important than d electron count in determining the geometry and metal−ligand bond distances of diphenylazodioxide complexes.",

author = "Emhoff, \{Kylin A.\} and Lakshmi Balaraman and Simpson, \{Sydney R.\} and Stromyer, \{Michael L.\} and Kalil, \{Haitham F.\} and Beemiller, \{James R.\} and Philipp Sikatzki and Eshelman, \{Teya S.\} and Salem, \{Ahmed M.H.\} and DeBord, \{Michael A.\} and Panzer, \{Matthew J.\} and Youngs, \{Wiley J.\} and Boyd, \{W. Christropher\}",

year = "2018",

month = nov,

day = "27",

doi = "10.1021/acsomega.8b01200",

language = "American English",

volume = "3",

journal = "ACS Omega",

}

TY - JOUR

T1 - Synthesis and Characterization of Cobalt(II) N,N′‑Diphenylazodioxide Complexes

AU - Emhoff, Kylin A.

AU - Balaraman, Lakshmi

AU - Simpson, Sydney R.

AU - Stromyer, Michael L.

AU - Kalil, Haitham F.

AU - Beemiller, James R.

AU - Sikatzki, Philipp

AU - Eshelman, Teya S.

AU - Salem, Ahmed M.H.

AU - DeBord, Michael A.

AU - Panzer, Matthew J.

AU - Youngs, Wiley J.

AU - Boyd, W. Christropher

PY - 2018/11/27

Y1 - 2018/11/27

N2 - Removal of chloride from CoCl 2 with TlPF 6 in acetonitrile, followed by addition of excess nitrosobenzene, yielded the eight-coordinate cobalt(II) complex salt [Co{Ph(O)NN(O)- Ph} 4 ](PF 6 ) 2 , shown by single-crystal X-ray analysis to have a distorted tetragonal geometry. The analogous treatment of the bipyridyl complex Co(bpy)Cl 2 yielded the mixed-ligand cobalt(II) complex salt [Co(bpy){Ph(O)NN(O)Ph} 2 ](PF 6 ) 2 , whose singlecrystal X-ray structure displays a trigonal prismatic geometry, similar to that of the iron(II) cation in the previously known complex salt [Fe{Ph(O)NN(O)Ph} 3 ](FeCl 4 ) 2 . The use of TlPF 6 to generate solvated metal complex cations from chloride salts or chlorido complexes, followed by the addition of nitrosobenzene, is shown to be a useful synthetic strategy for the preparation of azodioxide complex cations with the noncoordinating, diamagnetic PF 6 − counteranion. Coordination number appears to be more important than d electron count in determining the geometry and metal−ligand bond distances of diphenylazodioxide complexes.

AB - Removal of chloride from CoCl 2 with TlPF 6 in acetonitrile, followed by addition of excess nitrosobenzene, yielded the eight-coordinate cobalt(II) complex salt [Co{Ph(O)NN(O)- Ph} 4 ](PF 6 ) 2 , shown by single-crystal X-ray analysis to have a distorted tetragonal geometry. The analogous treatment of the bipyridyl complex Co(bpy)Cl 2 yielded the mixed-ligand cobalt(II) complex salt [Co(bpy){Ph(O)NN(O)Ph} 2 ](PF 6 ) 2 , whose singlecrystal X-ray structure displays a trigonal prismatic geometry, similar to that of the iron(II) cation in the previously known complex salt [Fe{Ph(O)NN(O)Ph} 3 ](FeCl 4 ) 2 . The use of TlPF 6 to generate solvated metal complex cations from chloride salts or chlorido complexes, followed by the addition of nitrosobenzene, is shown to be a useful synthetic strategy for the preparation of azodioxide complex cations with the noncoordinating, diamagnetic PF 6 − counteranion. Coordination number appears to be more important than d electron count in determining the geometry and metal−ligand bond distances of diphenylazodioxide complexes.

UR - https://engagedscholarship.csuohio.edu/scichem_facpub/497

U2 - 10.1021/acsomega.8b01200

DO - 10.1021/acsomega.8b01200

M3 - Article

VL - 3

JO - ACS Omega

JF - ACS Omega

ER -

Synthesis and Characterization of Cobalt(II) N,N′‑Diphenylazodioxide Complexes

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