Uebergangsmetallkomplexe mit Schwefelliganden XL. Synthese und Eigenschaften von RhI-, RhII- und RhIII-Komplexen mit den Schwefelliganden o-Benzoldithiolat(2-), o-Methylthiobenzolthiolat(1-) und 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecanat(2-) (=dttd2-) sowie CO und PPh3

Article abstract of DOI:10.1016/0022-328X(88)89048-X

In order to find new rhodium complexes whose metal centers are dominated by sulfur, , , 2, 2 and were treated with the ligands o-benzene dithiolate(2-), o-methyl thiobenzene thiolate(1-) and 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecanate(2-) (=dttd2-) to give NMe4 (1), NMe4 (3a), NMe4 (5), (2), (4), 2 (7), 2 (8), (9), (NMe4)3 (10) and (11), respectively.Whereas neither the RhII nor the RhIII complexes reacted with CO, phosphines or other small molecules, the RhI complexes are highly reactive.Compound 1 catalyses the oxygen transfer from DMSO to one of the PPh3 ligands to give O=PPh3 and Me2S; 1,3,and 5 can be interconverted under normal conditions by reaction with CO or PPh3.The structure of 4 was determined by X-ray crystallography and revealed planar, four coordinated Rh centres with the CO and the thiolate S atom occupying trans positions.