- Synthesis and properties of crown ether-modified posphines and their use as ligands in transition metal catalysts
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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-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 2, combined with IIIc and IIId, shows high activities toward catalytic hydrogenation of potassium and caesium cinnamates, respectively.Replacement of allyl bromide with powdered sodium or potassium iodide in benzene to give allyl iodide are catalyzed by (?-C3H5PdCl)2 in the presence of phosphines III.
- Okano, Tamon,Iwahara, Masahiro,Konishi, Hisatoshi,Kiji, Jitsuo
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p. 267 - 276
(2007/10/02)
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