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Citation: Chen Rongdi, Lin Huakuan, Gu Zongxin. LINEAR ENTHALPY RELATIONSHIPS BETWEEN HEATS OF FORMATION OF COMPLEX COMPOUNDS AND HEATS OF LIGANDS——Ⅲ. COPPER (Ⅱ) - 2,2′-BIPYRIDYL-COPPER (Ⅱ)-PHENANTHROLINE-N-(meta-SUBSTITUTED PHENYL) GLYCINES TERNARY SYSTEMS[J]. Acta Physico-Chimica Sinica, ;1986, 2(05): 452-456. doi: 10.3866/PKU.WHXB19860510 shu

LINEAR ENTHALPY RELATIONSHIPS BETWEEN HEATS OF FORMATION OF COMPLEX COMPOUNDS AND HEATS OF LIGANDS——Ⅲ. COPPER (Ⅱ) - 2,2′-BIPYRIDYL-COPPER (Ⅱ)-PHENANTHROLINE-N-(meta-SUBSTITUTED PHENYL) GLYCINES TERNARY SYSTEMS

1.
Department of Chemistry; Nankai University; Tianjin

Received Date: 28 May 1985
Available Online: 15 October 1986

The heats of formation of ternary complex compounds formed of copper(Ⅱ) with 2,2′-bipyridyl or 1,10-phenanthroline and N-(meta-substituted phenyl)glycines have been determinated by calorimatric method at 25 ℃ and Ⅰ=0.1 molL~(-1) (NaClO_4) in 30％(V/V) ethanol solution. By utilizing the data for the protonation of N-(meta-substituted phenyl) glycines determined previously and coupled with the heats of formation of ternary complex compounds, a linear enthalpy relationship: △H_M=Q-β△H_(L1) (r>0.99) with a nogative slope was obtained. In addition linear entropy relationships were also found to exist between the entropy changes on formation of ternary complex compounds and protonation of the second ligands.
The straight lines have approximately the same but negative slopes. The existence of negative slopes for linear enthalpy relationships would imply electrostatic interactions not important in the formation of thernary complex comounds, while back π bonding formation between metal ion and the first ligand and CFSE as well seem to play a significant role. Whereas negative linear entropy relationships might be accounted for by the change of entropy in configuration while the entropy of chelation and of solvation are almost parallel.
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