Synthesis of tris(cyclohexylisocyanide)bis(triphenylphosphine)cobalt(II) perchlorate. An example of unusual stabilization of the cobalt(II) oxidation state

Article abstract of DOI:10.1080/00945719708003157

A cobalt(II) complex with alkylisocyanide and triarylphosphine ligands is reported. Tris(cyclohexylisocyanide)bis(triphenylphosphine)cobalt(II) perchlorate, [Co(CNC₆H₁₁)₃(PPh₃) ₂](ClO₄)₂, was synthesized by PPh₃ ligand-substitution in [Co(CNC₆H¹¹)₄(AsPh₃) ₂](ClO₄)₂, in which the distribution of product among [Co(CNC₆H₁₁)₃(PPh3)2](ClO₄) ₂, [Co(CNC₆H₁₁)₃(PPh₃) ₂]ClO₄, [Co(OPPh₃)₄](ClO₄)₂, and unreacted [Co(CNC₆H₁₁)₄(AsPh₃) ₂](ClO₄)₂ was controlled in part by the concentration of PPh₃ and reaction time. [Co(CNC₆H₁₁)₃(PPh₃) ₂](ClO₄)₂ was also synthesized by AgClO₄ oxidation of [Co(CNC₆H₁₁)₃(PPh₃) ₂]ClO₄. [Co(CNC₆H₁₁)₃-(PPh₃) ₂](ClO₄)₂ is easily reduced to [Co(CNC₆H₁₁)₃(PPh₃) ₂]ClO₄ with N₂H₄.H₂O and decomposes into [Co(OPPh₃)₄](ClO₄)₂ on prolonged dissolution in CH₂Cl₂ solution, especially under UV (365 nm) irradiation. Physical properties for [Co(CNC₆H₁₁)₃(PPh₃) ₂](ClO₄)₂ and [Co(OPPh3)4](ClO4)2 support trigonal bipyramidal and tetrahedral solution and solid state stereochemistries, respectively, but both complexes have limited stability in most solvents.

Full text of DOI:10.1080/00945719708003157

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Synthesis and Reactivity in
Inorganic and Metal-Organic
Chemistry
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Synthesis of
tris(Cyclohexylisocyanide)bis(Triph
Perchlorate. An Example of
Unusual Stabilization of the
Cobalt(II) Oxidation State.
Clifford A. L. Becker a
a Department of Chemistry , University of
Botswana , P/Bag 0022, Gaborone, Botswana
Published online: 22 Aug 2006.
To cite this article: Clifford A. L. Becker (1997) Synthesis of
tris(Cyclohexylisocyanide)bis(Triphenylphosphine)Cobalt(II) Perchlorate. An
Example of Unusual Stabilization of the Cobalt(II) Oxidation State., Synthesis
and Reactivity in Inorganic and Metal-Organic Chemistry, 27:10, 1527-1542, DOI:
10.1080/00945719708003157
To link to this article: http://dx.doi.org/10.1080/00945719708003157
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