Journal of Organometallic Chemistry p. 267 - 276 (1988)
Update date:2022-08-03
Topics:
Okano, Tamon
Iwahara, Masahiro
Konishi, Hisatoshi
Kiji, Jitsuo
A novell series of crown ether-modified triarylphosphines, 1,2-diphenylphosphinino-2,3,5,6,8,9-hexahydro-1,4,7,10-benzotetraoxacyclodecin (IIIa) and its higher homolog (III) (common nomenclature is 3n-diphenylphosphinobenzo-<3n-crown-n>ethers (n=4,5,6 and 7)), is reported.The thermodynamic parameters for the extraction of alkali metal picrates are evaluated.Phosphines III (n=5 and 6) from 1:1 stoichiometric crown-type complexes with Na+ and K+.The observed extractability is in good agreement with the cavity size selectivity concept.The thermodynamic parameters ΔHo and TΔSo for the extractive complexation at 25 deg C are -63 to -58 kJ/mol and -41 to -35 kJ/mol, respectively, thus ΔGo is governed by the entalphy term.These phosphines are applied to reactions in liquid-liquid or liquid-solid phases, as the auxiliary ligands of homogenous palladium and rhodium catalysts.The catalytic activities correlate well with the extractibilities of the phyosphine ligands.The compound
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