Abstract
Nickel(11) complexes have
been prepared from 3-alkylacetylacetones, LH = CH3COCHRCOCH3
(R = Me, Et, Bu, and CH2Ph). The anhydrous complexes, NiL2, are red
and diamagnetic in the solid state and dissolve in toluene to give equilibrium
mixtures of monomeric, low-spin and trimeric, high-spin species. Equilibrium
constants have been obtained for the low-spin-high-spin equilibrium when R = Et
or CH2Ph. Reaction with pyridine in toluene solution gives the
adducts NiL2 py2, probably with Ni2L4
py as an intermediate. The relative stabilities of the low-spin and high-spin
forms of NiL2 are shown to depend not only on steric factors, but
also on electronic factors related to the acid dissociation constants of the ligands,
LH.
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