Synthesis of tris(Cyclohexylisocyanide)bis(Triphenylphosphine)Cobalt(II) Perchlorate. An Example of Unusual Stabilization of the Cobalt(II) Oxidation State
A cobalt(II) complex with alkylisocyanide and triarylphosphine ligands is reported. Tris(cyclohexylisocyanide)bis(triphenylphosphine)cobalt(II) perchlorate, [Co(CNC 6 H 11 ) 3 (PPh 3 ) 2 ](ClO 4 ) 2 , was synthesized by PPh 3 ligand-substitution in [Co(CNC 6 H 11 ) 4 (AsPh 3 ) 2 ](ClO 4 ) 2 in which...
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| Published in | Synthesis and reactivity in inorganic and metal-organic chemistry Vol. 27; no. 10; pp. 1527 - 1542 |
|---|---|
| Main Author | |
| Format | Journal Article |
| Language | English |
| Published |
Taylor & Francis Group
01.11.1997
|
| Online Access | Get full text |
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| Summary: | A cobalt(II) complex with alkylisocyanide and triarylphosphine ligands is reported. Tris(cyclohexylisocyanide)bis(triphenylphosphine)cobalt(II) perchlorate, [Co(CNC
6
H
11
)
3
(PPh
3
)
2
](ClO
4
)
2
, was synthesized by PPh
3
ligand-substitution in [Co(CNC
6
H
11
)
4
(AsPh
3
)
2
](ClO
4
)
2
in which the distribution of product among [Co(CNC
6
H
11
)
3
(PPh
3
)
2
](ClO
4
)
2
, [Co(CNC
6
H
11
)
3
(PPh
3
)
2
](ClO
4
, [Co(OPPh
3
)
4
](ClO
4
)
2
, and unreacted [Co(CNC
6
H
11
)
4
(AsPh
3
)
2
](ClO
4
)
2
was controlled in part by the concentration of PPh
3
and reaction time. [Co(CNC
6
H
11
)
3
(PPh
3
)
2
](ClO
4
)
2
was also synthesized by AgClO
4
oxidation of [Co(CNC
6
H
11
)
3
(PPh
3
)
2
]ClO
4
. [Co(CNC
6
H
11
)
3
(PPh
3
)
2
](ClO
4
)
2
is easily reduced to [Co(CNC
6
H
11
)
3
(PPh
3
)
2
]ClO
4
with N
2
H
4.
H
2
O and decomposes into [Co(OPPh
3
)
4
](ClO
4
)
2
on prolonged dissolution in CH
2
Cl
2
solution, especially under UV (365 nm) irradiation. Physical properties for [Co(CNC
6
H
11
)
3
(PPh
3
)
2
](ClO
4
)
2
and [Co(OPPh
3
)
4
](ClO
4
)
2
support trigonal bipyramidal and tetrahedral solution and solid state stereochemistries, respectively, but both complexes have limited stability in most solvents.
Referee I: T. Burkey
Referee II: K. M. DeArmond |
|---|---|
| ISSN: | 0094-5714 1532-2440 |
| DOI: | 10.1080/00945719708003157 |