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

Cleveland State University
University of Akron

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

Disciplines

Chemistry

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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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