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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Thermodynamics of metal-ligand bond formation. XXI. Base adducts of nickel(II) glyoximato complexes

DP Graddon and IA Siddiqi

Australian Journal of Chemistry 29(6) 1201 - 1207
Published: 1976

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 ΔHº and K (at 30ºC) for adducts of BF2-bridged complexes and for PBu3 adducts of H-bridged complexes (last entry) are: PY mpy pip PPh3 PBu3 Pbu3 -ΔHº (kJ mol-l) 29 31 35 23 43 42 K (1.mol-1) 3 5 80 4 800 60

https://doi.org/10.1071/CH9761201

© CSIRO 1976

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