Gezielte Synthese von Sulfinato‐O‐ und ‐S‐Komplexen einiger Übergangsmetalle, IV Bindungsisomerie bei Sulfinato‐Komplexen von Eisen(II), Kobalt(II) und Nickel(II)

Abstract

Treatment of the sulfinato-0.0' complexes l a -c with 2.2'-bipyridyl produces the ionic tris complexes 4a-c according to equation (4). The action of acetone results in the elimination of only 1 mole of 2.2'-bipyridyl from 4a-c to yield the linkage-isomeric sulfinato complexes of iron, cobalt, and nickel (3aO-cO and 3aS-cS) according to equation (5). 3aS can also be prepared in pyridine solution by the reaction of l a or 2a with 2.2'-bipyridyl according to equations (2) and (3). In pyridine at 115" the 0-isomers 3 a 0 and 3cO are converted irreversibly into the S-isomers 3aS and 3cS according to equation (6). 4a is transformed via 3 a 0 to the sulfinato-0.0' complex 2a if it is treated with acetone for a longer time. According to this result equation (1) is reversible from 2a via 3 a 0 to 4a for M = Fe. The linkage isomers 3aO-cO and 3aS-CS are characterized o n the basis of their i.r., electronic and M6ssbauer spectra as well as by magnetochemical investigations.Uber den ersten Fall von Bindungsisomerie des Sulfinato-Liganden berichteten bereits 1968 Deacon und Felder 2) am Beispiel des Phenylquecksilberbenzolsulfinats. Strukturelle und experimentelle Einzelheiten hieruber folgten in zwei weiteren Ver-1) 111. Mitteil.: E. Lindner, I.-P. Lorenz und G. Vitzthurn, Chem. Ber. 103, 3182 (1970).

Ethereal Hydroperoxides: Powerful Reagents for S-Oxygenation of Bridging Thiophenolate Functions

“…Both sulfinate complexes reveal two additional bands typical for S,O-bound μ 1,2 -ArSO 2 bridges. , The vibrations for 3 (1168 and 1015 cm –1 ) are slightly blue-shifted relative to those in 2 (1157 and 1011 cm –1 ). With the aid of DFT calculations (def2-TZVP/PBE0 level of theory), these vibrations can be attributed to the antisymmetric (ν a ) and symmetric (ν s ) stretching modes of the aryl sulfinates . The close correspondence between the calculated [1194 and 1057 cm –1 for 2 (Figure S3); 1189/1193 and 1061 cm –1 for 3 (Figure S6)] and experimental IR spectra of these sulfinate species suggests that the calculations provide a reasonable description of the geometric and electronic structures of 2 and 3 .…”