om960416e_si_001.pdf (608.51 kB)
Dicationic Nickel(II) Carbonyl Complexes Containing Tetradentate Ligands
journal contribution
posted on 1996-11-26, 00:00 authored by Alex Miedaner, Calvin J. Curtis, Sheryl A. Wander, Patricia A. Goodson, Daniel L. DuBoisThis article describes the preparation and spectroscopic
characterization of three dicationic
Ni(II) carbonyl complexes containing tripodal tetradentate
ligands. An X-ray diffraction
study of
[Ni(PP3E)(CO)](BF4)2
(where PP3E is
tris(2-(diethylphosphino)ethyl)phosphine)
has
been completed and confirms a trigonal bipyramidal structure with an
apical carbonyl ligand.
The binding of CO is weak and reversible. The stability of
these complexes is enhanced by
the small chelate bite imposed by the tetradentate ligands. The
electrochemical behavior
of these complexes depends on the nature of the donor atom trans to CO.
The [Ni(NP3E)(CO)]2+ (where NP3E is
tris(2-(diethylphosphino)ethyl)amine) cation undergoes
two reversible
one-electron reductions, whereas the corresponding tetraphosphine
cations undergo irreversible two-electron reductions.