Selective oxidation of thiacalix[4]arenes to the sulfinyl and sulfonyl counterparts and their complexation abilities toward metal ions as studied by solvent extraction

Abstract

Practical methods for the synthesis of sulfinyl-( 5, 6) and sulfonylcalix[4]arenes ( 7, 8) were provided by the selective oxidation of thiacalix[4]arenes ( 3, 4) with controlled amounts of an oxidant such as NaBO 3 or hydrogen peroxide under mild conditions. The coordination ability of thiacalix[4]arene 4 and the sulfinyl and sulfonyl analogs ( 6, 8) toward a wide variety of metal ions was investigated by solvent extraction and compared to that of the conventional methylene-bridged calix[4]arene 2. It was shown that the metal-ion selectivities of the sulfur-containing ligands 4, 6, and 8 were controlled by the oxidation state of the bridging sulfur moiety, which was best understood based on the hard and soft acid–base (HSAB) principle by assuming the critical role of the bridging groups in coordination to the metal center. Thus, 4 preferred soft metal ions by binding with S, while 8 did hard ones by ligating with sulfonyl O in addition to the adjacent two phenoxide oxygens, respectively. In good accordance with this hypothesis, 6 could bind to both hard and soft metal ions by using sulfinyl O and S, respectively. These made sharp contrast to the parent methylene-bridged 2, which could not essentially extract any metal ions at all, lacking lone pair electrons on the methylene bridge for coordination.