Convolution voltammetry of metal complexes

The application of convolution potential voltammetry to questions of metal complexation is described. Theoretical relations are derived to show that the stability constants may be directly related to the shift in the peak potential of the semiderivative wave, provided the complexes are labile. Equations are also given for inert and quasilabile complexes. Stability constants for the PbCl_x and CdCl_x systems are reported, illustrating the use of convolution techniques with linear scan voltammetry and with linear scan anodic stripping voltammetry. Advantages of convolution techniques are discussed.     

Synthesis of 2,4′-dioxospiro[indoline-3,2′-thiazolidine]-5′-acetic acids: X-ray structure of 1-benzyl-3′-(4-chlorophenyl)-2,4′-dioxospiro- [indoline-3,2′-thiazolidine]-5′-acetic acid

The title compounds have been prepared by the cyclocondensation of mercaptosuccinic acid with isatin-3-imines. The 1-benzyl derivatives have been synthesized by simultaneously reacting 1-benzylisatin, substituted anilines and mercaptosuccinic acid. The structure of the products has been confirmed by X-ray diffraction measurements.     

Synthesis of homoallylic chiral tertiary alcohols via chelation-controlled diastereoselective nucleophilic addition on alpha-alkoxyketones: application for the synthesis of the C(1)-C(11) subunit of 8-epi-fostriecin

[reaction: see text] Chiral beta-syn-alkoxyhomoallylic alcohols derived from alkoxyallylboration of aldehydes upon oxidation provided the corresponding chiral ketones. Chelation-controlled nucleophilic addition to these ketones occurred in a highly stereoselective manner to afford anti-homoallylic tertiary alcohols. This methodology has been applied for the synthesis of the C(1)-C(11) subunit of C(8)-epi-fostriecin.     

Facile synthesis of unsymmetrical benzotetrathiafulvalenes via cleavage of the corresponding hexathioorthooxalates

Unsymmetrical hexathioorthooxalates of types ($\text{1}$) and ($\text{2}$) undergo elimination of dialkyl disulfide on heating in an organic solvent; the reaction, which is catalyzed by acid, proceeds without fission of the central C:C bond and provides the first general, high yield synthesis of unsymmetrical benzotetrathiafulvalenes of types ($\text{3}$) and ($\text{4}$).