Thiocarbonyl complexes of iron VIII. Reaction of Fe(CO) 4CS with the halogens Cl 2, Br 2 and I 2

Abstract

The halogens Br 2 and I 2 convert the thiocarbonyl complex Fe(CO) 4CS ( 1) by oxidative addition into the corresponding complexes Fe(CO) 3(CS)X 2 ( 3:XBr, I). Treatment of 3 at −80 °C with two equivalents of PPh 3 yields the thiocarbonyl complexes Fe(CO)(CS)(PPh 3) 2X 2 ( 4). The action of Cl 2 on 1 produces an unidentified black insoluble material containing terminal CO and CS groups. The compounds have been characterized by elemental analysis, IR, 31P NMR and mass spectroscopy. Based on the spectroscopic results, a cis arrangement of the halogen atoms is discussed.