MULTIPLE REACTION PATHWAYS IN THE REACTIONS OF CARBONYLFERRATE ANIONS WITH CHALCOGENS, AND WITH CHALCOGEN-CONTAINING ANIONS

Article abstract of DOI:10.1016/0022-328X(85)88074-8

The reactions of ^- or ^- with either sulphite or polysulfide all yield a mixture of Fe2S2(CO)6, Fe3S2(CO)9, Fe3S(CO)10 and Fe3S(CO)9(SO), together with Fe3(CO)12 in the reactions with sulphite.Fe2S2(CO)6 readily undergoes cluster expansion with ^- to yield Fe3S2(CO)9, but further reaction to give Fe3S(CO)10, or reconversion to Fe2S2(CO)6 is not possible.In contrast, ^- with selenite yields Fe3S2(CO)9 only, but ^- yields not only Fe3Se2(CO)9 but also Fe2Se2(CO)6 and Fe3(CO)12.With high molar ratios of elemental sulphur or selenium, ^- yields pure Fe2E2(CO)6 (E = S or Se) but with an equimolar amount sulphur a mixture of Fe3S2(CO)9, Fe3(CO)12, Fe3S(CO)10 and Fe3S(CO)9(SO), with no Fe2S2(CO)6, is obtained: use of an equimolar amount of selenium yieds both Fe2Se2(CO)6 and Fe3Se2(CO)9.The formation and interconversions of iron-chalcogen carbonyl clusters are discussed.