SCHEDULED MAINTENANCE
Stabilization of cobalt(I) by the tripodal ligands tris(2-pyridyl)methane and tris(2-pyridyl)phosphine. Structural, spectroscopic and ab initio studies of the [CoL2]n+ species
Abstract
The nature of bonding in a series of complexes
[CoL
2
]
n
+
[L = the tripodal
ligand tris(2-pyridyl)methane or tris(2-pyridyl)phosphine,
n = 1–3] has been investigated by
single-crystal X-ray diffraction, X-ray absorption and electronic
spectroscopy and density functional theory ab initio
calculations. The structural studies reveal that the cobalt ions each
exist in a distorted octahedral geometry defined by six N-donor atoms;
the cations are all centrosymmetric. In both series of complexes the
bond lengths
Co
I
–N ≈ Co
II
–N
> Co
III
–N. Data from the various
studies indicate that the ‘cobalt(I)’ state of
the complex
[Co{X(C
5
H
4
N-2)
3
}
2
]
+
(X = CH or P) is better described by the
d
8
cobalt(I)–ligand formulation rather than
as d
7
cobalt(II)–ligand radical.
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