Abstract
Bis(glyoximato)nicke1(11)
complexes and their BF2-bridged derivatives react with Lewis bases
in non-donor solvents forming low-spin 1 : 1 adducts. Thermodynamic data are
reported for formation of adducts of glyoximato
complexes with PBu3 and of BF2-bridged complexes with
pyridine (py), 4-methylpyridine (mpy), piperidine (pip), tributylphosphine, triphenylphosphine,
ethane-1,2-diyi- bis(diphenylphosphine) and tetrahydrothiophen. Adduct stability is increased by BF2-bridging;
in the Pbu3 adducts this is due to entropy factors. Variation of
alkyl groups in the glyoxinie has only a small
effect, but replacement of alkyl by Ph or H increases adduct stability while
lowering enthalpy of adduct formation. Average values of ΔH� and K (at 30�C)
for adducts of BF2-bridged complexes and for PBu3 adducts
of H-bridged complexes (last entry) are:
PY mpy pip PPh3 PBu3 Pbu3
-ΔH� (kJ mol-l) 29
31 35
23 43
42
K (1.mol-1) 3 5 80
4 800
60
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